A method and apparatus for selectively oxidizingcarbonmonoxide in a hydrogen rich feed stream. The method comprises mixing a feed stream consisting essentially of hydrogen, carbon dioxide, water and carbonmonoxide with a first predetermined quantity of oxygen (air). The temperature of the mixed feed/oxygen stream is adjusted in a first the heat exchanger assembly (20) to a first temperature. The mixed feed/oxygen stream is sent to reaction chambers (30,32) having an oxidation catalyst contained therein. The carbonmonoxide of the feed stream preferentially absorbs on the catalyst at the first temperature to react with the oxygen in the chambers (30,32) with minimal simultaneous reaction of the hydrogen to form an intermediate hydrogen rich process stream having a lower carbonmonoxide content than the feed stream. The elevated outlet temperature of the process stream is carefully controlled in a second heat exchanger assembly (42) to a second temperature above the first temperature. The process stream is then mixed with a second predetermined quantity of oxygen (air). The carbonmonoxide of the process stream preferentially reacts with the second quantity of oxygen in a second stage reaction chamber (56) with minimal simultaneous reaction of the hydrogen in the process stream. The reaction produces a hydrogen rich product stream having a lower carbonmonoxide content than the process stream. The product stream is then cooled in a third heat exchanger assembly (72) to a third predetermined temperature. Three or more stages may be desirable, each with metered oxygen injection.

A method and composition for the complete oxidation of carbonmonoxide and/or hydrocarbon compounds. The method involves reacting the carbonmonoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

A method and composition are disclosed for the complete oxidation of carbonmonoxide and/or hydrocarbon compounds. The method involves reacting the carbonmonoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Protect yourself and your family from the deadly effects of carbonmonoxide--a colorless, odorless poisonous gas. This publication describes the warning signs of carbonmonoxide exposure and includes a home safety checklist....

Several different catalytic reactions must be carried out in order to convert hydrocarbons (or alcohols) into hydrogen for use as a fuel for polyelectrolyte membrane (PEM) fuel cells. Each reaction in the fuel-processing sequence has a different set of characteristics, which influences the type of catalyst support that should be used for that particular reaction. A wide range of supports are being evaluated for the various reactions in the fuel-processing scheme, including porous and non-porous particles, ceramic and metal straight-channel monoliths, and ceramic and metal monolithic foams. These different types of support have distinctly different transport characteristics. The best choice of support for a given reaction will depend on the design constraints for the system, e.g., allowable pressure drop, and on the characteristics of the reaction for which the catalyst is being designed. Three of the most important reaction characteristics are the intrinsic reaction rate, the exothermicity/endothermicity of the reaction, and the nature of the reaction network, e.g., whether more than one reaction takes place and, in the case of multiple reactions, the configuration of the network. Isotopic transient kinetic analysis was used to study the surface intermediates. The preferential oxidation of low concentrations of carbonmonoxide in the presence of high concentrations of hydrogen (PROX) is an important final step in most fuel processor designs. Data on the behavior of straight-channel monoliths and foam monolith supports will be presented to illustrate some of the factors involved in choosing a support for this reaction.

Research continued on the metabolism of carbonmonoxide by Rhodospirillum rubrum. This report discusses progress on the activity, induction, inhibition, and spectroscopic analysis of the enzyme CarbonMonoxide Dehydrogenase. (CBS)

Quantitative hydroxyl radical concentrations and primary soot particle sizes have been determined in the soot oxidation regions of axisymmetric diffusion flames burning methane, methane/butane, and methane/1-butene in air at atmospheric pressure. The total carbon flow rate was held constant in these flames while the maximum amount of soot varied by a factor of seven along the centerline. Laser-induced fluorescence measurements of OH were placed on an absolute basis by calibration against earlier absorption results. The primary size measurements of the soot particles were made using thermophoretic sampling and transmission electron microscopy. OH concentrations are greatly reduced in the presence of soot particles. Whereas large super-equilibrium ratios are observed in the high-temperature reaction zones in the absence of soot, the OH concentrations approach equilibrium values when the soot loading is high. The diminished OH concentrations are found to arise from reactions with the soot particles and only to a minor degree from lower temperatures due to soot radiation losses. Analysis of the soot oxidation rates computed from the primary particle size profiles as a function of time along the flame centerlines shows that OH is the dominant oxidizer of soot, with O[sub 2] making only a small contribution. Higher collision efficiencies of OH reactions with soot particles are found for the flames containing larger soot concentrations at lower temperatures. A comparison of the soot and CO oxidation rates shows that although CO is inherently more reactive than soot, the soot successfully competes with CO for OH and hence suppresses CO oxidation for large soot concentrations.

Catalysis by single isolated atoms of precious metals has attracted much recent interest since it promises the ultimate economy in atom efficiency. Previous reports have been confined to reducible oxide supports such as FeOx, TiO2 or CeO2. Here we show that isolated Pd atoms can be stabilized on industrially relevant gamma-alumina supports. At low Pd loadings (?0.5 wt%) these catalysts contain exclusively atomically dispersed Pd species. The addition of lanthanum-oxide to the alumina, long known for its ability to improve alumina stability, is found to also help in the stabilization of isolated Pd atoms. Aberration-corrected scanning transmission electron microscopy (AC-STEM) confirms the presence of intermingled Pd and La on the gamma-alumina surface. Operando X-ray absorption spectroscopy, performed on Pd/La-alumina and Pd/gamma-alumina (0.5 wt% Pd) demonstrates the presence of catalytically active atomically dispersed ionic Pd in the Pd/La-doped gamma-alumina system. CO oxidation reactivity measurements show onset of catalytic activity at 40 ?C, indicating that the ionic Pd species are not poisoned by CO. The reaction order in CO and O2 is positive, suggesting a reaction mechanism that is different from that on metallic Pd. The catalyst activity is lost if the Pd species are reduced to their metallic form, but the activity can be regenerated by oxidation at 700 ?C in air. The high-temperature stability of these ionic Pd species on commercial alumina supports makes this catalyst system of potential interest for low-temperature exhaust treatment catalysts.

Title: Catalytic Hydrogenation of CarbonMonoxide and Olefin Oxidation Grant No. DE-FG02-86ER13615 PI: Wayland, B. B. (wayland@sas.upenn.edu) Abstract Development of new mechanistic strategies and catalyst materials for activation of CO, H2, CH4, C2H4, O2, and related substrates relevant to the conversion of carbonmonoxide, alkanes, and alkenes to organic oxygenates are central objectives encompassed by this program. Design and synthesis of metal complexes that manifest reactivity patterns associated with potential pathways for the hydrogenation of carbonmonoxide through metallo-formyl (M-CHO), dimetal ketone (M-C(O)-M), and dimetal dionyl (M-C(O)-C(O)-M) species is one major focus. Hydrocarbon oxidation using molecular oxygen is a central goal for methane activation and functionalization as well as regioselective oxidation of olefins. Discovery of new reactivity patterns and control of selectivity are pursued through designing new metal complexes and adjusting reaction conditions. Variation of reaction media promotes distinct reaction pathways that control both reaction rates and selectivities. Dimetalloradical diporphyrin complexes preorganize transition states for substrate reactions that involve two metal centers and manifest large rate increases over mono-metalloradical reactions of hydrogen, methane, and other small molecule substrates. Another broad goal and recurring theme of this program is to contribute to the thermodynamic database for a wide scope of organo-metal transformations in a range of reaction media. One of the most complete descriptions of equilibrium thermodynamics for organometallic reactions in water and methanol is emerging from the study of rhodium porphyrin substrate reactions in aqueous and alcoholic media. Water soluble group nine metalloporphyrins manifest remarkably versatile substrate reactivity in aqueous and alcoholic media which includes producing rhodium formyl (Rh-CHO) and hydroxy methyl (Rh-CH2OH) species. Exploratory directions for this program include expending new strategies for anti-Markovnikov addition of water, alcohols, and amines with olefins, developing catalytic reactions of CO to give formamides and formic esters, and evaluating the potential for coupling reactions of CO to produce organic building blocks.

Research continued on the metabolism of carbonmonoxide by Rhodospirillum rubrum. This report discusses progress on the activity, induction, inhibition, and spectroscopic analysis of the enzyme CarbonMonoxide Dehydrogenase. (CBS)

The invention involves the synergistic effect of the specific catalytic constituents on a specific series of carriers for the methanation of carbonmonoxide in the presence of sulfur at relatively high temperatures and at low steam to gas ratios in the range of 0.2:1 or less. This effect was obtained with catalysts comprising the mixed sulfides and oxides of nickel and chromium supported on carriers comprising magnesium aluminate and magnesium silicate. Conversion of carbonmonoxide to methane was in the range of from 40 to 80%. Tests of this combination of metal oxides and sulfides on other carriers and tests of other metal oxides and sulfides on the same carrier produced a much lower level of conversion.

Carbonmonoxide sensors suitable for use in hydrogen feed streams and methods of use thereof are disclosed. The sensors are palladium metal/insulator/semiconductor (Pd-MIS) sensors which may possess a gate metal layer having uniform, Type 1, or non-uniform, Type 2, film morphology. Type 1 sensors display an increased sensor response in the presence of carbonmonoxide while Type 2 sensors display a decreased response to carbonmonoxide. The methods and sensors disclosed herein are particularly suitable for use in proton exchange membrane fuel cells (PEMFCs).

At present carbonmonoxide sensing devices are readily available for many industrial applications. The sensors used in these devices include electrochemical sensors, semiconductor sensors, calorimetric detectors and infra red detectors. From these devices the electrochemical sensors are of specific interest because of their high selectivity and low power consumption. This makes them suitable for use in battery operated devices, e.g. for domestic safety. However, their relatively high price and frequent need for recalibration seriously hamper their utilisation on a large scale. The relatively high price of electrochemical CO sensors is caused by the complexity of fabrication. They are composed of a cylindrical housing, with one end the counter and reference electrodes, and on the other the working electrode. The electrodes are made out of Teflon bonded platinum black on a Teflon substrate and the electrolyte is a sulfuric acid solution. The aim of this work was to develop electrochemical CO sensors, that are small and cheaper than the existing products. The approach concentrated on three main aspects: (a) simplification of the device assembly by investigating the of using a planar sensor design, (b) use of mass production compatible fabrication, and (c) replacement of the sulfuric acid.

Carbonmonoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbonmonoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO.sub.2, from which a relatively pure methane product may be obtained. While carbonmonoxide-containing gas streams having hydrogen or water present therein can be used only the carbonmonoxide available after reaction with said hydrogen or water is decomposed to form said active surface carbon. Although hydrogen or water will be converted, partially or completely, to methane that can be utilized in a combustion zone to generate heat for steam production or other energy recovery purposes, said hydrogen is selectively removed from a CO--H.sub.2 -containing feed stream by partial oxidation thereof prior to disproportionation of the CO content of said stream.

This invention relates to a high molecular weight terpolymer of ethylene, sulfur dioxide and carbonmonoxide stable to 280.degree. C. and containing as little as 36 mol % ethylene and about 41-51 mol % sulfur dioxide; and to the method of producing said terpolymer by irradiation of a liquid and gaseous mixture of ethylene, sulfur dioxide and carbonmonoxide by means of Co-60 gamma rays or an electron beam, at a temperature of about 10.degree.-50.degree. C., and at a pressure of about 140 to 680 atmospheres, to initiate polymerization.

, SCIAMACHY CO total column retrievals are of sufficient quality to provide useful new information]. Ground-based FTIR measurements provide high quality total column measurements but have very limitedQuantitative analysis of SCIAMACHY carbonmonoxide total column measurements A. T. J. de Laat,1,2 A

Adsorption of Nitrogen Monoxide and CarbonMonoxide on Copper-Exchanged ZSM-5: A Cluster study on the adsorption of NO and CO in Cu-ZSM-5, using an ab initio embedded cluster methodology are small for adsorption energies of CO and NO. For adsorption of CO, the calculated binding energy of 32

Progress since the initiation of this two year award on May 1, 1988, has been divided into two areas for reporting purposes. We have been working on ideas described in the proposal submitted two years ago, and simultaneously we initiated chemistry in a distinct area in order to provide a springboard for the current proposal. Efforts directed toward reductive coupling of carbonmonoxide have continued to focus on carbyne species as the central figure in coupling reactions. At the same time we have attempted to prepare intermediate oxidation state metal imido complexes with an eye to synthetic applications of nitrene transfer reagents. The results of carbyne chemistry, electrophilic addition reactions of anionic carbonyl and isonitrile complexes, and carbyne-carbonyl coupling reactions will be presented in this progress report, while the work with nitrene complexes will be included as preliminary results in the text of the accompanying proposal. The description of published work will be brief in this report; greater detail will be provided for unpublished material.

Two devices, an occupational carbonmonoxide (CO) dosimeter (LOCD), and an indoor air quality (IAQ) passive sampler were developed for use in population-based CO exposure assessment studies. CO exposure is a serious public health problem in the U.S., causing both morbidity and mortality (lifetime mortality risk approximately 10{sup -4}). Sparse data from population-based CO exposure assessments indicate that approximately 10% of the U.S. population is exposed to CO above the national ambient air quality standard. No CO exposure measurement technology is presently available for affordable population-based CO exposure assessment studies. The LOCD and IAQ Passive Sampler were tested in the laboratory and field. The palladium-molybdenum based CO sensor was designed into a compact diffusion tube sampler that can be worn. Time-weighted-average (TWA) CO exposure of the device is quantified by a simple spectrophotometric measurement. The LOCD and IAQ Passive Sampler were tested over an exposure range of 40 to 700 ppm-hours and 200 to 4200 ppm-hours, respectively. Both devices were capable of measuring precisely (relative standard deviation <20%), with low bias (<10%). The LOCD was screened for interferences by temperature, humidity, and organic and inorganic gases. Temperature effects were small in the range of 10{degrees}C to 30{degrees}C. Humidity effects were low between 20% and 90% RH. Ethylene (200 ppm) caused a positive interference and nitric oxide (50 ppm) caused a negative response without the presence of CO but not with CO.

We compare the observational and theoretical spectra of the $\\Delta v$ = 2 CO bands in a range of M dwarfs. We investigate the dependence of theoretical spectra on effective temperatures as well as carbon abundance. In general we find that the synthetic CO bands fit the observed data extremely well and are excellent diagnostics. In particular the synthetic spectra reasonably match observations and the best fit temperatures are similar to those found by empirical methods. We also examine the \\CDC isotopic ratio. We find that fundamental $^{13}$CO bands around 2.345 and 2.375 $\\mu$m are good discriminators for the \\CDC ratio in M dwarfs. The 2.375 $\\mu$m is more useful because it doesn't suffer such serious contamination by water vapour transitions. Our current dataset does not quite have the wavelength coverage to perform a reliable determination of the \\CDC ratio in M dwarfs. For this we recommend observing the region 2.31--2.40 $\\mu$m at a resolution of better than 1000. Alternatively the observational problems of contamination by water vapour at 2.345 $\\mu$m maybe solved by observing at resolutions of around 50000. We also investigated the possibility of using the $\\Delta v$ = 1 CO bands around 4.5 $\\mu$m. We find that the contamination due to water vapour is even more of a problem at these wavelengths.

Fuel processing systems for low temperature polymer electrolyte membrane (PEM) fuel cell systems require control of the carbonmonoxide concentration to less than 100 ppm to 10 ppm in the anode feed. Conventional hydrocarbon fuel processors use a water-gas shift (WGS) reactor to react CO with water to form H2 and reduce the CO concentration. The CO conversion is limited by equilibrium at the outlet temperature of the WGS reactor. The WGS outlet CO concentration can range from over 1% to 2000 ppm depending on the system and its operating parameters. At these concentrations, CO poisons low temperature PEM fuel cells and the concentrations needs to be reduced further.

An experimental rig program has been conducted with the objective of evaluating the combustion performance of a family of fuel gases based on a mixture of hydrogen and carbonmonoxide. These gases, in addition to being members of a family, were also representative of those secondary fuels that could be produced from coal by various gasification schemes. In particular, simulated Winkler, Lurgi, and Blue-water low and medium energy content gases were used as fuels in the experimental combustor rig. The combustor used was originally designed as a low NOx rich-lean system for burning liquid fuels with high bound nitrogen levels. When used with the above gaseous fuels this combustor was operated in a lean-lean mode with ultra long residence times. The Bluewater gas was also operated in a rich-lean mode. The results of these tests indicate the possibility of the existence of an ''optimum'' gas turbine hydrogen - carbonmonoxide based secondary fuel. Such a fuel would exhibit low NOx and high efficiency over the entire engine operating range. It would also have sufficient stability range to allow normal light-off and engine acceleration. Solar Turbines Incorporated would like to emphasize that the results presented here have been obtained with experimental rig combustors. The technologies generated could, however, be utilized in future commercial gas turbines.

produced could be stored, e.g. by geological sequestration, making the overall process “carbon-neutral”, or “carbon-negative” when biomass is used as fuel. In addition, the hydrogen produced during the oxidation of FexO and metallic Fe in steam can be kept... Kinetics of the reduction of wüstite by hydrogen and carbonmonoxide for the chemical looping production of hydrogen Wen Liu a,n, Jin Yang Lim b, Marco A. Saucedo a, Allan N. Hayhurst b, Stuart A. Scott a, J.S. Dennis b a Department of Engineering...

Carbonmonoxide-containing gas streams are converted to methane by a cyclic, essentially two-step process in which said carbonmonoxide is disproportionated to form carbon dioxide and active surface carbon deposited on the surface of a catalyst, and said carbon is reacted with steam to form product methane and by-product carbon dioxide. The exothermic heat of reaction generated in each step is effectively removed during each complete cycle so as to avoid a build up of heat from cycle-to-cycle, with particularly advantageous techniques being employed for fixed bed, tubular and fluidized bed reactor operations.

The invention provides vacuum swing adsorption processes that produce an essentially carbonmonoxide-free hydrogen or helium gas stream from, respectively, a high-purity (e.g., pipeline grade) hydrogen or helium gas stream using one or two adsorber beds. By using physical adsorbents with high heats of nitrogen adsorption, intermediate heats of carbonmonoxide adsorption, and low heats of hydrogen and helium adsorption, and by using vacuum purging and high feed stream pressures (e.g., pressures of as high as around 1,000 bar), pipeline grade hydrogen or helium can purified to produce essentially carbonmonoxide -free hydrogen and helium, or carbonmonoxide, nitrogen, and methane-free hydrogen and helium.

Carbonmonoxide dehydrogenase from Clostridium thermoaceticum catalyzes two reactions involving redox chemistry (the reversible oxidation Of CO to C02, and the synthesis of acetyl-CoA) using three types of Ni and Fe-S structures called the A-, B...

We hypothesized that circulating microparticles (MPs) play a role in pro-inflammatory effects associated with carbonmonoxide (CO) inhalation. Mice exposed for 1 h to 100 ppm CO or more exhibit increases in circulating MPs derived from a variety of vascular cells as well as neutrophil activation. Tissue injury was quantified as 2000 kDa dextran leakage from vessels and as neutrophil sequestration in the brain and skeletal muscle; and central nervous system nerve dysfunction was documented as broadening of the neurohypophysial action potential (AP). Indices of injury occurred following exposures to 1000 ppm for 1 h or to 1000 ppm for 40 min followed by 3000 ppm for 20 min. MPs were implicated in causing injuries because infusing the surfactant MP lytic agent, polyethylene glycol telomere B (PEGtB) abrogated elevations in MPs, vascular leak, neutrophil sequestration and AP prolongation. These manifestations of tissue injury also did not occur in mice lacking myeloperoxidase. Vascular leakage and AP prolongation were produced in naïve mice infused with MPs that had been obtained from CO poisoned mice, but this did not occur with MPs obtained from control mice. We conclude that CO poisoning triggers elevations of MPs that activate neutrophils which subsequently cause tissue injuries. - Highlights: • Circulating microparticles (MPs) increase in mice exposed to 100 ppm CO or more. • MPs are lysed by infusing the surfactant polyethylene glycol telomere B. • CO-induced MPs cause neutrophil activation, vascular leak and CNS dysfunction. • Similar tissue injuries do not arise with MPs obtained from air-exposed, control mice.

Influence of Co/Mo Ratio on Synthesis of Single-Walled Carbon Nanotubes from CarbonMonoxide, Bunkyo-ku, Tokyo 113-8656 Co and Mo are often used as catalysts for the catalytic chemical vapor in synthesizing random, vertical and parallel aligned SWNTs on Co and Mo dip-coated quartz substrates from carbon

The compound, [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic {alpha}-olefins, with carbonmonoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbonmonoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbonmonoxide to form optically active, isotactic poly(1,5-ketone).

The compound, [Pd(Me-DUPHOS)(MeCN).sub.2 ](BF.sub.4).sub.2, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic .alpha.-olefins, with carbonmonoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbonmonoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbonmonoxide to form optically active, isotactic poly(1,5-ketone)

The objective of the project is to develop the technology capable of capturing all carbonmonoxide and carbon dioxide from natural gas fueled Solid Oxide Fuel Cell (SOFC) system. In addition, the technology to electrochemically oxidize any remaining carbonmonoxide to carbon dioxide will be developed. Success of this R&D program would allow for the generation of electrical power and thermal power from a fossil fuel driven SOFC system without the carbon emissions resulting from any other fossil fueled power generationg system.

from forest clearing and biofuels. Thus CO is a global pollutant with a variety of sources. CO has and transport. CO AMS 2000 subject classifications: Carbonmonoxide; satellite data; Bayesian hierarchi- cal and the transport of surface emissions but also in determining budgets for other chemical constituents. 1

Six hundred and ninety New Jersey ambulances were monitored for carbonmonoxide (CO); 27 per cent had CO levels of 10 ppm or more greater than ambient air in the breathing zone of the patient. Twenty-nine of these ambulances had levels of at least 35 ppm greater than ambient air. Results indicate that a CO exposure problem exists in ambulances.

A molten metal reactor for converting a carbon material and steam into a gas comprising hydrogen, carbonmonoxide, and carbon dioxide is disclosed. The reactor includes an interior crucible having a portion contained within an exterior crucible. The interior crucible includes an inlet and an outlet; the outlet leads to the exterior crucible and may comprise a diffuser. The exterior crucible may contain a molten alkaline metal compound. Contained between the exterior crucible and the interior crucible is at least one baffle.

A study of solid salts containing cationic complexes of palladium(II) with neutral, weakly complexing ligands resulted in the discovery of the palladium(II)-acetamide-tetrafluoroborate reagent, in which acetamide is present in 20-fold molar excess. It was found that a successful reagent of this type must have a ligand that complexes palladium(II) weakly, but more strongly than does water, with water available for subsequent reaction. Carbonmonoxide appears to coordinate with the palladium(II)-acetamide complex, which then reacts with water to form, simultaneously, palladium(O) metal that is black, carbon dioxide, and hydrogen ion. The reagent is described as a visual warning device for the present of carbonmonoxide. 5 figs., 1 tab.

The possible trends for atmospheric carbonmonoxide in the next 100 yr have been illustrated using a coupled atmospheric chemistry and climate model driven by emissions predicted by a global economic development model. ...

Hazardous air pollutants, including benzene, are generated by the incomplete combustion of fuels. Organic compound emissions, which are generally products of incomplete combustion, are reduced by promoting high quality combustion, for example by controlling furnace exit temperatures and establishing minimum residence times. Monitoring carbonmonoxide (CO) emissions is important since the amount of carbonmonoxide emitted represents the quality of combustion which in turn represents the amount of hazardous air pollutants being generated. Total hydrocarbon (THC) emissions are also related to the quality of combustion. Recently the Wisconsin Department of Natural Resources (DNR) measured the benzene and total hydrocarbon emissions from two large industrial wood fired boilers. These boilers are located at Tenneco Packaging, a container board manufacturing facility in northern Wisconsin. Temperature, oxygen and carbonmonoxide concentrations were sampled continuously by Tenneco Packaging`s emission monitoring system. The Department`s team used an organic vapor analyzer to continuously measure concentrations of total hydrocarbons (THC). The Department`s team also used a modified USEPA Method 18 sampling train to capture organic vapors for subsequent analysis by gas chromatography. The data show correlations between benzene and carbonmonoxide, and between benzene and THC concentrations. The emissions sampling occurred both upstream of the particulate emissions control system as well as at the stack. The CO variations during actual boiler operation appeared to be well correlated with changes in boiler steam load. That is, increases in CO generally accompanied a change, either up or down, in boiler load. Lower concentrations of CO were associated with stable combustion, as indicated by periods of constant or nearly constant boiler load.

This paper will describe air permitting regulations that apply to a new cogeneration facility or the modification of any existing facility. The permitting depends on several factors including the attainment status of the emitted criteria pollutants within the project area, with the facility classified as either a ``major new source`` or a ``major modification``. Depending on the attainment status of a given pollutant, either the Prevention of Significant Deterioration (PSD) or the Non-attainment area (NAA) regulations (Title I of the Clean Air Act Amendments of 1990) will apply for that pollutant. Since the greatest percentage of emissions generated by a gas turbine are nitrogen oxides (ozone precursors) and carbonmonoxide this paper presents an overview of clean air regulations pertinent to those areas of the country that are designated as attaining the National Ambient Air Quality Standards (NAAQS) for sulphur dioxide (SO{sub 2}), particulate matter (PM), nitrogen oxides (NO{sub x}) and lead (Pb), and as areas of nonattainment for ozone (O{sub 3}) and carbonmonoxide (CO). A hypothetical case is presented and all the environmental issues such as applicability of PSD and NAA regulations, available pollution offsets, and air quality compliance requirements for a modification to an existing facility located in a serious ozone and moderate carbonmonoxide non-attainment area will be illustrated.

Carbonmonoxide is produced in a fast quench reactor. The production of carbonmonoxide includes injecting carbon dioxide and some air into a reactor chamber having a high temperature at its inlet and a rapidly expanding a reactant stream, such as a restrictive convergent-divergent nozzle at its outlet end. Carbon dioxide and other reactants such as methane and other low molecular weight hydrocarbons are injected into the reactor chamber. Other gas may be added at different stages in the process to form a desired end product and prevent back reactions. The resulting heated gaseous stream is then rapidly cooled by expansion of the gaseous stream.

Hydrogen and carbonyl sulfide are produced by a process comprising contracting gaseous hydrogen sulfide with gaseous carbonmonoxide in the presence of a heteropolymolybdate or tungstate complex. Use of these catalysts reduce the amount of by-product carbon dioxide and methane formation and thus enhance the make of hydrogen and carbonyl sulfide.

An electrocatalyst is provided for use in a fuel cell that has low platinum loading and a high tolerance to carbonmonoxide poisoning. The fuel cell anode includes an electrocatalyst that has a conductive support material, ruthenium nanoparticles reduced in H.sub.2 and a Group VIII noble metal in an amount of between about 0.1 and 25 wt % of the ruthenium nanoparticles, preferably between about 0.5 and 15 wt %. The preferred Group VIII noble metal is platinum. In one embodiment, the anode can also have a perfluorinated polymer membrane on its surface.

Laboratory rats were exposed (a) to experimental concentrations of carbonmonoxide in air at ambient temperature, (b) to elevated temperature atmospheres from 40 deg C to 60 deg C, and (c) to selected carbonmonoxide (CO) concentrations at the elevated temperatures in (b). The incapacitating potency of each of the environments was evaluated by measurements of time-to-incapacitation (t sub i) as a function of CO concentration and/or temperature; incapacitation was defined operationally as loss of ability to walk inside a motor-driven, rotating cage enclosed in an exposure chamber. Comparison of data from the combined (CO + elevated temperature) exposures and exposures to CO and elevated temperatures alone indicated than incapacitation occurred earlier when CO inhalation was combined with a whole-body, elevated temperature environment than was observed for the same exposure parameters applied individually. No evidence for a synergistic effect was noted. An empirical equation was derived that allows the calculation of a predicted t sub i for combinations of CO and temperature within the rangers utilized in the experimental exposures.

-strengths compared to the overtone bands near 2.3 ?m and 1.55 ?m. The mid-IR sensor was applied to a high-pressure combustor to determine the time-history of carbonmonoxide and compare it to other measured combustor parameters to fully characterize the combustor’s...

Homogeneous Charge Compression Ignitions (HCCI) engines show promise as an alternative to Diesel engines, yet research remains: development of practical HCCI engines will be aided greatly by accurate modeling tools. A novel detailed chemical kinetic model that incorporates information from a computational fluid mechanics code has been developed to simulate HCCI combustion. This model very accurately predicts many aspects of the HCCI combustion process. High-resolution computational grids can be used for the fluid mechanics portion of the simulation, but the chemical kinetics portion of the simulation can be reduced to a handful of computational zones (for all previous work 10 zones have been used). While overall this model has demonstrated a very good predictive capability for HCCI combustion, previous simulations using this model have tended to underpredict carbonmonoxide emissions by an order of magnitude. A factor in the underprediction of carbonmonoxide may be that all previous simulations have been conducted with 10 chemical kinetic zones. The chemistry that results in carbonmonoxide emissions is very sensitive to small changes in temperature within the engine. The resolution in temperature is determined directly by the number of zones. This paper investigates how the number of zones (i.e. temperature resolution) affects the model's prediction of hydrocarbon and carbonmonoxide emissions in an HCCI engine. Simulations with 10, 20, and 40 chemical kinetic zones have been conducted using a detailed chemical kinetic mechanism (859 species, 3606 reactions) to simulate an isooctane fueled HCCI engine. The results show that 10-zones are adequate to resolve the hydrocarbon emissions, but a greater numbers of zones are required to resolve carbonmonoxide emissions. Results are also presented that explore spatial sources of the exhaust emissions within the HCCI engine combustion chamber.

We report the detection of carbonmonoxide (CO) emission from the young supernova remnant Cassiopeia A (Cas A) at wavelengths corresponding to the fundamental vibrational mode at 4.65 micron. We obtained AKARI Infrared Camera spectra towards 4 positions which unambiguously reveal the broad characteristic CO ro-vibrational band profile. The observed positions include unshocked ejecta at the center, indicating that CO molecules form in the ejecta at an early phase. We extracted a dozen spectra across Cas A along the long 1 arcmin slits, and compared these to simple CO emission models in Local Thermodynamic Equilibrium to obtain first-order estimates of the excitation temperatures and CO masses involved. Our observations suggest that significant amounts of carbon may have been locked up in CO since the explosion 330 years ago. Surprisingly, CO has not been efficiently destroyed by reactions with ionized He or the energetic electrons created by the decay of the radiative nuclei. Our CO detection thus implies that...

A solar photospheric "thermal profiling" analysis is presented, exploiting the infrared rovibrational bands of carbonmonoxide (CO) as observed with the McMath-Pierce Fourier transform spectrometer (FTS) at Kitt Peak, and from above the Earth's atmosphere by the Shuttle-borne ATMOS experiment. Visible continuum intensities and center-limb behavior constrained the temperature profile of the deep photosphere, while CO center-limb behavior defined the thermal structure at higher altitudes. The oxygen abundance was self consistently determined from weak CO absorptions. Our analysis was meant to complement recent studies based on 3-D convection models which, among other things, have revised the historical solar oxygen (and carbon) abundance downward by a factor of nearly two; although in fact our conclusions do not support such a revision. Based on various considerations, an oxygen abundance of 700+/-100 ppm (parts per million relative to hydrogen) is recommended; the large uncertainty reflects the model sensitivity of CO. New solar isotopic ratios also are reported for 13C, 17O, and 18O.

by anodic oxidation of titanium foil followed with O2 and CO annealing were employed as matrices nanostructures by means of acidic anodization of titanium foils.14,15 The diameters and lengths of the TNT can bone­implant inter- actions. In addition, doping with nitrogen, carbon, and boron has been reported

The use of small, personal monitors as instruments for air pollution data acquisition, storage, and retrieval presents a new set of monitoring considerations. Portability, ruggedness, power supplies, and data capture are functions to be addressed in designing personal monitoring systems. The emphasis herein is on the data capture function. This paper describes experiences using the Hewlett-Packard HP-41CV system as a data management system interfaced with personal carbonmonoxide monitors (General Electric CarbonMonoxide Detector, Model 15EC53CO3). In general, the HP-41CV proved to be reliable, adaptable, and easy to use. Problems with the monitor power source (battery failure) were more frequent than with the HP-41CV itself. Using the HP-41CV for the specific data collection requirements of the Washington Microenvironment Study is a focal point of this presentation.

This report describes the analysis and conclusion of an investigation of the carbonmonoxide emissions resulting from Sandia National Laboratories and Department of Energy (DOE) commuter and on-base traffic for the Clean Air Act (CAA) Conformity Determination. Albuquerque/Bernalillo County was classified as a nonattainment area by the Environmental Protection Agency. Nonattainment area is an area which is shown by monitored data or which is calculated by air quality modeling to exceed any National Ambient Air Quality Standard (NAAQS) for the pollutant. Albuquerque/Bernalillo County exceeds the NAAQS for carbonmonoxide and ozone. The Conformity Determination was needed to complete the CAA Title V Permitting process for SNL and the DOE. The analysis used the EPA approved MOBILE5a CarbonMonoxide (CO) emissions modeling program. This analysis will provide a baseline for mobile sources to allow Sandia to estimate any future activity and how that activity will impact CO emissions. The General Conformity Rule (AQCR 43) requires that operations which will increase CO emissions in nonattaimnent or maintenance areas such as Bernalillo County undergo conformity analyses to determine whether or not they will impact ambient air quality in the area.

Absorption lines from water, methane and carbonmonoxide are detected in the atmosphere of exoplanet HR8799b. A medium-resolution spectrum presented here shows well-resolved and easily identified spectral features from all three molecules across the K band. The majority of the lines are produced by CO and H2O, but several lines clearly belong to CH4. Comparisons between these data and atmosphere models covering a range of temperatures and gravities yield log mole fractions of H2O between -3.09 and -3.91, CO between -3.30 and -3.72 and CH4 between -5.06 and -5.85. More precise mole fractions are obtained for each temperature and gravity studied. A reanalysis of H-band data, previously obtained at similar spectral resolution, results in a nearly identical water abundance as determined from the K-band spectrum. The methane abundance is shown to be sensitive to vertical mixing and indicates an eddy diffusion coefficient in the range of 10^6 to 10^8 cm^2 s^-1, comparable to mixing in the deep troposphere of Jupite...

The data from consecutive surveys of the Tucson Epidemiologic Study (1981-1988) were used to evaluate the relationship in cigarette smokers of respiratory symptoms and pulmonary function to tar, nicotine, and carbonmonoxide (CO) yields of the cigarette. There were 690 subjects who reported smoking regularly in at least one survey, over age 15. After adjustment for intensity and duration of smoking and for depth of inhalation, the risk of chronic phlegm, cough, and dyspnea were not related to the tar and nicotine yields. In 414 subjects with pulmonary function tested in at least one of the three surveys the spirometric indices used were significantly related to the daily dose of tar, nicotine, and CO (product of the cigarette yield and daily number of cigarettes smoked). The effects were more pronounced for past than for current doses. However, the differentiation of pulmonary function due to various yields of cigarettes was small in comparison to the difference in pulmonary function between smokers and nonsmokers.

The effects of surface structure on the CO hydrogenation reaction were investigated by comparing the activity and selectivity of submonolayer cobalt deposited on W(110) and W(100) with that of carbonyl-derived Co/alumina catalysts of varying dispersion. The structure, stability, surface electronic properties, and chemisorptive properties of vapor deposited cobalt overlayers (0-4 ML) on W(110) and W(100) were studied by Auger electron spectroscopy, low electron diffraction, work function changes, and temperature programmed desorption of cobalt, hydrogen, and carbonmonoxide. The chemisorptive properties of the cobalt overlayers are quite different from those of bulk cobalt surfaces. The Co/W surface have highly strained and different geometries but have similar CO hydrogenation activity. The activity nearly matches that of the highly active, highly reduced Co/alumina catalysts, showing that the activity of cobalt surfaces is independent of surface structure. The specific activity of carbonyl-derived catalysts appears to be more closely related to the extent of reduction and the support dehydroxylation temperatures than to the dispersion. Thus, the chemical nature of the support surface is the controlling factor in determining the specific activity of supported cobalt catalysts. CO hydrogenation on cobalt is neither primary nor secondary structure sensitive.

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n+1).gtoreq.x.gtoreq.O and for olefinic hydrocarbons: 2n.gtoreq.x.gtoreq.O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Coal will likely continue to be a dominant component of power generation in the foreseeable future. This project addresses the issue of environmental compliance for two important pollutants: NO{sub x} and mercury. Integration of emission control units is in principle possible through a Low Temperature Selective Catalytic and Adsorptive Reactor (LTSCAR) in which NO{sub x} removal is achieved in a traditional SCR mode but at low temperature, and, uniquely, using carbonmonoxide as a reductant. The capture of mercury is integrated into the same process unit. Such an arrangement would reduce mercury removal costs significantly, and provide improved control for the ultimate disposal of mercury. The work completed in this project demonstrates that the use of CO as a reductant in LTSCR is technically feasible using supported manganese oxide catalysts, that the simultaneous warm-gas capture of elemental and oxidized mercury is technically feasible using both nanostructured chelating adsorbents and ceria-titania-based materials, and that integrated removal of mercury and NO{sub x} is technically feasible using ceria-titania-based materials.

The present invention generally relates to catalyst systems and methods for oxidation of carbonmonoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbonmonoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

An all-solid-state continuous-wave (cw) laser system for mid-infrared absorption measurements
of the carbonmonoxide (CO) molecule has been developed and demonstrated. The single-mode, tunable
output of an external-cavity ...

Higher, i.e. C{sub 2{sup +}}, alcohols are desired as gasoline additives, feedstocks for producing ethers and as alternative fuels for automobiles. In all cases, the backbone branching of an alcohol improves octane rating, which is essential for good engine performance. These types of branched, higher alcohols are the desired products for a process converting synthesis gas, a CO and H{sub 2} mixture, often generated from coal gasification. Based on this premise, promoted ZnCr oxide catalysts appear to be as one of the best avenues for further investigation. Once this investigation is complete, a natural extension is to replace the Cr in the ZnCr oxide catalyst with Mo and W, both in the same elemental triad with Cr. Mo has already been shown as an active HAS catalyst, both on a SiO{sub 2} support and in the MoS{sub 2} form. The three catalyst combinations, ZnMo, ZnW, and MnCr oxides will be tested in the stirred autoclave system. However, if none of the three indicate any comparable activity and/or selectivity toward higher alcohols as compared with other HAS catalysts, then an investigation of the effects of Cs promotion on the ZnCr oxide methanol catalysts will be executed.

, this work includes the history of the fundamental reactions of automotive catalysts including carbonmonoxide (CO), hydrogen (H2) and nitric oxide (NO) oxidation on a widely used material formulation (platinum catalyst on alumina washcoat). A detailed report...

Black Carbon in the Soil Carbon Cycle: Is it an Oxidation Resistant End-Product? Simone Submitted on December 21, 2007 Reviewed April 1, 2008 Abstract Black carbon (BC) is a very oxidation, charcoal, and soot. Due to its high recalcitrance, black carbon might act as a long-term carbon sink

OAK-B135 The structure of the active-site C-cluster in CO dehydrogenase from Carboxythermus hydrogenoformans includes a {mu}{sup 2}-sulfide ion bridged to the Ni and unique Fe, while the same cluster in enzymes from Rhodospirillum rubrum (CODH{sub Rr}) and Moorella thermoacetica (CODH{sub Mt}) lack this ion. This difference was investigated by exploring the effects of sodium sulfide on activity and spectral properties. Sulfide partially inhibited the CO oxidation activity of CODH{sub Rr} and generated a lag prior to steady-state. CODH{sub Mt} was inhibited similarly but without a lag. Adding sulfide to CODH{sub Mt} in the C{sub red1} state caused the g{sub av} = 1.82 EPR signal to decline and new features to appear, including one with g = 1.95, 1.85 and (1.70 or 1.62). Removing sulfide caused the g{sub av} = 1.82 signal to reappear and activity to recover. Sulfide did not affect the g{sub av} = 1.86 signal from the C{sub red2} state. A model was developed in which sulfide binds reversibly to C{sub red1}, inhibiting catalysis. Reducing this adduct causes sulfide to dissociate, C{sub red2} to develop, and activity to recover. Using this model, apparent K{sub I} values are 40 {+-} 10 nM for CODH{sub Rr} and 60 {+-} 30 {micro}M for CODH{sub Mt}. Effects of sulfide are analogous to those of other anions, including the substrate hydroxyl group, suggesting that these ions also bridge the Ni and unique Fe. This proposed arrangement raises the possibility that CO binding labilizes the bridging hydroxyl and increases its nucleophilic tendency towards attacking Ni-bound carbonyl.

This report describes a process to recover steel plant waste oxides to be used in the production of hot metal. The process flowsheet used at the pilot plant. Coal/coke breeze and iron ore pellets/waste oxides are charged into the smelting reactor. The waste oxides are either agglomerated into briquettes (1 inch) using a binder or micro-agglomerated into pellets (1/4 inch) without the use of a binder. The iron oxides dissolve in the slag and are reduced by carbon to produce molten iron. The gangue oxides present in the raw materials report to the slag. Coal charged to the smelter is both the fuel as well as the reductant. Carbon present in the waste oxides is also used as the fuel/reductant resulting in a decrease in the coal requirement. Oxygen is top blown through a central, water-cooled, dual circuit lance. Nitrogen is injected through tuyeres at the bottom of the reactor for stirring purposes. The hot metal and slag produced in the smelting reactor are tapped at regular intervals through a single taphole using a mudgun and drill system. The energy requirements of the process are provided by (i) the combustion of carbon to carbonmonoxide, referred to as primary combustion and (ii) the combustion of CO and H{sub 2} to CO{sub 2} and H{sub 2}O, known as postcombustion.

An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbonmonoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbonmonoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbonmonoxide can be converted to hydrogen by the water gas shift reaction.

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbonmonoxide.

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbonmonoxide.

An enhanced method for the post processing, i.e. oxidation or stabilization, of carbon materials including, but not limited to, carbon foams, carbon fibers, dense carbon-carbon composites, carbon/ceramic and carbon/metal composites, which method requires relatively very short and more effective such processing steps. The introduction of an "oxygen spill over catalyst" into the carbon precursor by blending with the carbon starting material or exposure of the carbon precursor to such a material supplies required oxygen at the atomic level and permits oxidation/stabilization of carbon materials in a fraction of the time and with a fraction of the energy normally required to accomplish such carbon processing steps. Carbon based foams, solids, composites and fiber products made utilizing this method are also described.

A method of removing nitrogen monoxide from a nitrogen monoxide-containing gas, which method comprises: (a) contacting a nitrogen oxide-containing gas with an aqueous solution of water soluble organic compound-iron ion chelate of the formula: ##STR1## wherein the water-soluble organic compound is selected from compounds of the formula: ##STR2## wherein: R is selected from hydrogen or an organic moiety having at least one polar functional group; Z is selected from oxygen, sulfur, or --N--A wherein N is nitrogen and A is hydrogen or lower alkyl having from one to four carbon atoms; and M is selected from hydrogen, sodium or potassium; and n is 1 or 2, in a contacting zone for a time and at a temperature effective to reduce the nitrogen monoxide. These mixtures are useful to provide an unexpensive method of removing NO from gases, thus reducing atmospheric pollution from flue gases.

Laboratory and industrial research now underway at the sintering plant of AO Mittal Steel Temirtau is focusing on the preparation of fuel of optimal granulometric composition, the replacement of coke fines, and the adaptation of fuel-input technology so as to reduce fuel consumption and toxic emissions without loss of sinter quality.

Methanol fuel processing generates hydrogen for low-temperature, PEM fuel cell systems now being considered for transportation and other applications. Although liquid methanol fuel is convenient for this application, existing fuel processing techniques generate contaminants that degrade fuel cell performance. Through mathematical models and laboratory experiments chemical processing is described that removes CO and other contaminants from the anode feed stream.

Flow Obstruction Smokers may suffer from a spectrum of respiratory disorders ranging from the near universal morning cough to respiratory failure. Much difficulty in understanding the natural history of these diseases results from the different...

Highlights: ? Tungsten oxide deposited on carbon nanowalls by hot filament chemical vapor deposition technique. ? This composite has two-dimensional uniform morphology with a crystalline structure of monoclinic tungsten trioxide. ? Surface photoelectric voltage measurements show that this product has photoresponse properties. - Abstract: In the present work we present a simple approach for coupling tungsten oxide with carbon nanowalls. The two-dimensional carbon nanowalls with open boundaries were grown using plasma enhanced hot filament chemical vapor deposition, and the subsequent tungsten oxide growth was performed in the same equipment by direct heating of a tungsten filament. The tungsten oxide coating is found to have uniform morphology with a crystalline structure of monoclinic tungsten trioxide. Surface photoelectric voltage measurements show that this product has photoresponse properties. The method of synthesis described here provides an operable route to the production of two-dimensional tungsten oxide nanocomposites.

A catalyst for the oxidation of heavy metal contaminants, especially mercury (Hg), in an effluent stream is presented. The catalyst facilitates removal of mercury through the oxidation of elemental Hg into mercury (II) moieties. The active component of the catalyst is partially combusted coal, or "Thief" carbon, which can be pre-treated with a halogen. An untreated Thief carbon catalyst can be self-promoting in the presence of an effluent gas streams entrained with a halogen.

Oxy-fuel combustion in natural gas power generation is a technology of growing interest as it provides the most efficient means of carbon capture. Since all the emissions from these power plants are sequestered, there are ...

Finely divided carbon is manufactured by a process producing a gaseous stream containing carbonmonoxide by reacting coal and air in a slagging ash gasifier, separating carbonmonoxide from the gaseous mixture, and disproportionating the carbonmonoxide to produce finely divided carbon and carbon dioxide, the latter of which is recycled to the gasifier.

The oxidation of dust and flakes collected from the DIII-D tokamak, and various commercial dust specimens, has been measured at 350 ºC and 2.0 kPa O2 pressure. Following an initial small mass loss, most of the commercial dust specimens showed very little effect due to O2 exposure. Similarly, dust collected from underneath DIII-D tiles, which is thought to comprise largely Grafoil™ particulates, also showed little susceptibility to oxidation at this temperature. However, oxidation of the dust collected from tile surfaces has led to ~ 18% mass loss after 8 hours; thereafter, little change in mass was observed. This suggests that the surface dust includes some components of different composition and/or structure – possibly fragments of codeposited layers. The oxidation of codeposit flakes scraped form DIII-D upper divertor tiles showed an initial 25% loss in mass due to heating in vacuum, and the gradual loss of 30-38% mass during the subsequent 24 hours exposure to O2. This behavior is significantly different from that observed for the oxidation of thinner DIII-D codeposit specimens which were still adhered to tile surfaces, and this is thought to be related to the low deuterium content (D/C ~ 0.03 – 0.04) of the flakes.

The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

Li-air batteries have attracted substantial interest for their high theoretical specific energies, but the oxygen reduction reaction by Li (Li-ORR) that occurs at the carbon cathode remains poorly understood. Periodic density functional theory calculations have been performed to examine the Li-ORR on several model carbon structures, including the graphite(0001) basal plane, the (8,0) single-wall nanotube, the armchair-type edge, and a di-vacancy in the basal plane. The inertness of the basal plane limits the reversible potential of O{sub 2} reduction to 1.1 V, and slightly higher to 1.2 V on the curved nanotube. The armchair edge and di-vacancy are highly reactive and significantly oxidized at ambient conditions to various CO{sub x} groups, which are reduced by Li via redox mechanisms at 1.2-1.4 V. These CO{sub x} groups can also catalyze O{sub 2} reduction at up to 2.3 V (an overpotential of 0.4 V vs. the calculated equilibrium potential for bulk Li{sub 2}O{sub 2} formation) by chelating and stabilizing the LiO{sub 2} intermediate. The Li-ORR on graphitic carbon, if via concerted Li{sup +}/e{sup -} transfer and involving carbon, lithium, and oxygen only, is therefore expected to initiate with the smallest overpotential at under-coordinated carbon centers that are oxidized at ambient conditions.

A Mathematical Model of OxideÃ?Carbon Composite Electrode for Supercapacitors Hansung Kim for the general application of supercapacitors consisting of an oxide/carbon composite electrode. The model takes. Supercapacitors can be divided into two categories: electric double-layer capacitors and pseudocapacitors

The HRS Oil Shale Retort process consists of a pyrolysis section which converts kerogen of the shale to liquid and gaseous products, and a combustion section which burns residual carbon on the shale to heat the process. Average gas concentrations of selected gas phase species were determined from data measured at several placed on the combustion system of the Lawrence Livermore National Laboratory Hot-Recycled-Solids Retort Pilot Plant for representative rich and lean shale runs. The data was measured on-line and in real time by on-line meters (CO{sub 2}, CO, O{sub 2}), mass spectrometry (CO{sub 2}, O{sub 2}, H{sub 2}O, NO, CH{sub 4}, SO{sub 2}, N{sub 2} and Ar), and Fourier transform infrared spectroscopy (CO{sub 2}, CO, H{sub 2}O, NO, N{sub 2}O, NO{sub 2}, CH{sub 4}, SO{sub 2}, NH{sub 3}, and HCN). For both the rich and leans shale runs, the Lift-Pipe Combustor (LFT) exhibited gas concentrations (sampled at the exit of the LFT) indicative of incomplete combustion and oxidation; the Delayed-Fall Combustor (DFC) exhibited gas concentrations (sampled at the annulus and the exit of the DFC) indicative of much more complete combustion and oxidation. The Fluidized-Bed Combustor exhibited gas concentrations which were controlled to a large extent by the injection atmosphere of the FBC. High levels of nitrogen oxides and low levels of CO were detected when full air injection was used, while high levels of CO and low levels of nitrogen-oxides were detected with partial N{sub 2} injection. Sequential sampling limitations and nitrogen balances are also discussed.

There has been increasing interest in electrochemical capacitors as energy storage systems because of their high power density and long cycle life, compared to battery devices. According to the mechanism of energy storage, there are two types of electrochemical capacitors. One type is based on double layer (dl) formation due to charge separation, and the other type is based on a faradaic process due to redox reactions. Sol-gel derived high surface area carbon-ruthenium xerogels were prepared from carbonized resorcinol-formaldehyde resins containing an electrochemically active form of ruthenium oxide. The electrochemical capacitance of these materials increased with an increase in the ruthenium content indicating the presence of pseudocapacitance associated with the ruthenium oxide undergoing reversible faradaic redox reactions. A specific capacitance of 256 F/g (single electrode) was obtained from a carbon xerogel containing 14 wt% Ru, which corresponded to more than 50% utilization of the ruthenium. The double layer accounted for 40% of this capacitance. This material was also electrochemically stable, showing no change in a cyclic voltammogram for over 2,000 cycles.

A process to remove carbon dioxide from a gas stream using a cross-flow, or a moving-bed reactor. In the reactor the gas contacts an active material that is an alkali-metal compound, such as an alkali-metal carbonate, alkali-metal oxide, or alkali-metal hydroxide; or in the alternative, an alkaline-earth metal compound, such as an alkaline-earth metal carbonate, alkaline-earth metal oxide, or alkaline-earth metal hydroxide. The active material can be used by itself or supported on a substrate of carbon, alumina, silica, titania or aluminosilicate. When the active material is an alkali-metal compound, the carbon-dioxide reacts with the metal compound to generate bicarbonate. When the active material is an alkaline-earth metal, the carbon dioxide reacts with the metal compound to generate carbonate. Spent sorbent containing the bicarbonate or carbonate is moved to a second reactor where it is heated or treated with a reducing agent such as, natural gas, methane, carbonmonoxide hydrogen, or a synthesis gas comprising of a combination of carbonmonoxide and hydrogen. The heat or reducing agent releases carbon dioxide gas and regenerates the active material for use as the sorbent material in the first reactor. New sorbent may be added to the regenerated sorbent prior to subsequent passes in the carbon dioxide removal reactor.

Influence of reduced carbon emissions and oxidation on the distribution of atmospheric CO2 carbon emission and oxidation processes in deriving inversion estimates of CO2 surface fluxes. Citation carbon emissions and oxidation on the distribution of atmospheric CO2: Implications for inversion

it is a clean and efficient alternative to the use of coal instead of combustion. The gasification process are important in carbon gasification processes as well as in carbon single-wall nanotubes formation from CO disproportionation reaction. In the case of gasification, adsorption of CO blocks the active sites

The global market for wireless sensor networks in 2010 will be valued close to $10 B, or 200 M units. TPL, Inc. is a small Albuquerque based business that has positioned itself to be a leader in providing uninterruptible power supplies in this growing market with projected revenues expected to exceed $26 M in 5 years. This project focused on improving TPL, Inc.'s patent-pending EnerPak{trademark} device which converts small amounts of energy from the environment (e.g., vibrations, light or temperature differences) into electrical energy that can be used to charge small energy storage devices. A critical component of the EnerPak{trademark} is the supercapacitor that handles high power delivery for wireless communications; however, optimization and miniaturization of this critical component is required. This proposal aimed to produce prototype microsupercapacitors through the integration of novel materials and fabrication processes developed at New Mexico Technology Research Collaborative (NMTRC) member institutions. In particular, we focused on developing novel ruthenium oxide nanomaterials and placed them into carbon supports to significantly increase the energy density of the supercapacitor. These improvements were expected to reduce maintenance costs and expand the utility of the TPL, Inc.'s device, enabling New Mexico to become the leader in the growing global wireless power supply market. By dominating this niche, new customers were expected to be attracted to TPL, Inc. yielding new technical opportunities and increased job opportunities for New Mexico.

The present invention relates to a method of removing of nitrogen monoxide from a nitrogen monoxide-containing gas which method comprises contacting a nitrogen oxide-containing gas with an aqueous solution of water soluble organic compound-iron ion chelate complex. The NO absorption efficiency of ferrous urea-dithiocarbamate and ferrous diethanolamine-xanthate as a function of time, oxygen content and solution ph is presented. 3 figs., 1 tab.

This progress report covers the two broad areas of research addressed during the period since May 1, 1990. As proposed in 1989, studies of carbyne transformations have been pursued with a variety of carbyne substituents. Perhaps the most noteworthy carbyne results are also the simplest: preparation and properties of the parent M{triple_bond}CH unit. The other topic addressed with DOE support has metal nitrene chemistry as the cornerstone. Publications with iron, tungsten and copper complexes reflect our efforts to access intermediate oxidation state metal nitrene monomers. This new thrust was a central theme of the proposal submitted in 1989, and progress to date is sufficiently encouraging that detailed plans for expanding our nitrene project are an integral part of the accompanying proposal. References in this progress report are kept to a minimum; extensive references in the papers cited here place the work in perspective relative to the literature landscape.

A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO{sub 2} and wustite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbonoxidation and wustite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wustite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wustite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (> 1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbonoxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbonoxidation state and carbon number (nC).

The covalent, surface functionalization of graphene oxide with the malononitrile anion has been demonstrated. Once installed, these surface-bound “molecular lynchpins” can be chemically modified to increase the solubility ...

The carbon-carbon laminates examined in this research program are two-dimensional, eight harness satin weaves with boron carbide (B4C) inhibitor particles and a multi-layer silicon carbide (SiC) coating. These inhibitor ...

Electrochemical Double Layer Capacitors (EDLC) for high energy and power density applications, based on glassy carbon (GC) electrodes, are being developed in this laboratory. In the context of this project, GC sheets were oxidized and investigated with Small Angle X-ray Scattering (SAXS), Electrochemical Impedance Spectroscopy (EIS) and Nitrogen Gas Adsorption (BET). During oxidation on active film with open pores is built on the surface of the GC. Upon oxidation, the internal volumetric surface area of the active film decreases, whereas the volumetric electrochemical double layer capacitance increases. The authors show that this effect is correlated with the opening, the growth and the coalescence of the pores.

The interfacial bond characteristics between carbon fiber and a cement matrix, in high temperature fiber-reinforced cementitious composite systems, can be improved by the oxidative treatment of the fiber surfaces. Compositions and the process for producing the compositions are disclosed.

The interfacial bond characteristics between carbon fiber and a cement matrix, in high temperature fiber-reinforced cementitious composite systems, can be improved by the oxidative treatment of the fiber surfaces. Compositions and the process for producing the compositions are disclosed. 2 figs.

A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

The authors successfully synthesized titanium oxide (TiO{sub 2}) nanopowder with visible-light photocatalytic ability by low-pressure flat-flame metal organic chemical vapor condensation method. In order to confirm that carbon doping is a viable mechanism for the visible-light absorption of the powder prepared by this method, they modify the process by total exclusion of nitrogen usage to eliminate the nitrogen doping possibility. Since nitrogen is avoided in the process, the visible-light absorption cannot be due to nitrogen doping. They also found that the nanopowder formed has a single phase of anatase. Thus the nanopowder does not have anatase/rutile interface, and the authors can eliminate the possibility of visible-light absorption by the anatase/rutile interface. The visible-light absorption should thus be resort to the carbon doping. X-ray photoelectron spectroscopy studies show the presence of several carbon related bonds except Ti-C bond. This suggests that the carbon does not incorporate into the TiO{sub 2} crystal and should locate on the surface of the nanopowder. Thus the carbon species act as a visible-light sensitizer for the TiO{sub 2} as a photocatalyst. Among all carbon bonds the C-C bond is believed to be responsible for the light absorption, since all other carbon related bonds are not chromophores. The visible-light TiO{sub 2} photocatalysis induced by carbon doping is confirmed and explained.

The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

An electro-catalytic oxidation device (ECOD) for the removal of contaminates, preferably carbonaceous materials, from an influent comprising an ECOD anode, an ECOD cathode, and an ECOD electrolyte. The ECOD anode is at a temperature whereby the contaminate collects on the surface of the ECOD anode as a buildup. The ECOD anode is electrically connected to the ECOD cathode, which consumes the buildup producing electricity and carbon dioxide. The ECOD anode is porous and chemically active to the electro-catalytic oxidation of the contaminate. The ECOD cathode is exposed to oxygen, and made of a material which promotes the electro-chemical reduction of oxygen to oxidized ions. The ECOD electrolyte is non-permeable to gas, electrically insulating and a conductor to oxidized. The ECOD anode is connected to the fuel reformer and the fuel cell. The ECOD electrolyte is between and in ionic contact with the ECOD anode and the ECOD cathode.

Porous nickel oxide/multiwalled carbon nanotubes (NiO/MWNTs) composite material was synthesized using sodium dodecyl phenyl sulfate as a soft template and urea as hydrolysis-controlling agent. Scanning electron microscopy (SEM) results show that the as-prepared nickel oxide nanoflakes aggregate to form a submicron ball shape with a porous structure, and the MWNTs with entangled and cross-linked morphology are well dispersed in the porous nickel oxide. The composite shows an excellent cycle performance at a high current of 2 A g{sup -1} and keeps a capacitance retention of about 89% over 200 charge/discharge cycles. A specific capacitance approximate to 206 F g{sup -1} has been achieved with NiO/MWNTs (10 wt.%) in 2 M KOH electrolyte. The electrical conductivity and the active sites for redox reaction of nickel oxide are significantly improved due to the connection of nickel nanoflakes by the long entangled MWNTs.

The characteristics of radiation that is reflected from carbon deposits and oxidation formations on highly reflective surfaces such as Mo/Si mirrors can be quantified and employed to detect and measure the presence of such impurities on optics. Specifically, it has been shown that carbon deposits on a Mo/Si multilayer mirror decreases the intensity of reflected HeNe laser (632.8 nm) light. In contrast, oxide layers formed on the mirror should cause an increase in HeNe power reflection. Both static measurements and real-time monitoring of carbon and oxide surface impurities on optical elements in lithography tools should be achievable.

Highly active, durable and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions including water splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel iron layered double hydroxide nanoplates on mildly oxidized multi-walled carbon nanotubes. Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-layered double hydroxide. The nanoplates were covalently attached to a network of nanotubes, affording excellent electrical wiring to the nanoplates. The ultra-thin Ni-Fe layered double hydroxide nanoplates/carbon nanotube complex was found to exhibit unusually high electro-catalytic activity and stability for oxygen evolution and outperformed commercial precious metal Ir catalysts.

The cycling and oxidation pathways of organic carbon were investigated at a single shallow water estuarine site in Trinity Bay, Texas, the uppermost lobe of Galveston Bay, during November 2000. Radio-isotopes were used to estimate sediment mixing and accumulation rates, and benthic chamber and pore water measurements were used to determine sediment-water exchange fluxes of oxygen, nutrients and metals, and infer carbonoxidation rates.

Adsorption of carbon dioxide from gas streams at temperatures in the range of 300 to 500.degree. C. is carried out with a solid adsorbent containing magnesium oxide, preferably promoted with an alkali metal carbonate or bicarbonate so that the atomic ratio of alkali metal to magnesium is in the range of 0.006 to 2.60. Preferred adsorbents are made from the precipitate formed on addition of alkali metal and carbonate ions to an aqueous solution of a magnesium salt. Atomic ratios of alkali metal to magnesium can be adjusted by washing the precipitate with water. Low surface area adsorbents can be made by dehydration and CO.sub.2 removal of magnesium hydroxycarbonate, with or without alkali metal promotion. The process is especially valuable in pressure swing adsorption operations.

Ethanol is a renewable fuel that can be used as an additive to gasoline (or its substitute) with the advantage of octane enhancement and reduced carbonmonoxide exhaust emissions. However, on Ethanol is a renewable fuel that can be used as an additive to gasoline (or its substitute) with the advantage of octane enhancement and reduced carbonmonoxide exhaust emissions. However, on the standard three-way catalysts, the conversion of unburned ethanol is low because both ethanol and some of its partially oxidized derivatives are highly resistant to oxidation. A combination of first-principles density-functional theory (DFT) based calculations and in-situ diffuse reflectance infrared spectroscopy (DRIFTS) analysis was applied to uncover some of the fundamental phenomena associated with ethanol oxidation on Pt containing catalysts. In particular, the objective was to analyze the role of the oxide (i.e., ?-Al2O3 or SiO2) substrate on the ethanol oxidation activity. The results showed that Pt nanoparticles trap and accumulate oxygen at their surface and perimeter sites and play the role of “stoves” that burn ethanol molecules and their partially oxidized derivatives to the “final” products. The ?-Al2O3 surfaces provided higher mobility of the fragments of ethanol molecules than the SiO2 surface and hence increased the supply rate of these objects to the Pt particles. This will in turn produce a higher conversion rate of unburned ethanol.and some of its partially oxidized derivatives are highly resistant to oxidation. A combination of first-principles density-functional theory (DFT) based calculations and in-situ diffuse reflectance infrared spectroscopy (DRIFTS) analysis was applied to uncover some of the fundamental phenomena associated with ethanol oxidation on Pt containing catalysts. In particular, the objective was to analyze the role of the oxide (i.e., ?-Al2O3 or SiO2) substrate on the ethanol oxidation activity. The results showed that Pt nanoparticles trap and accumulate oxygen at their surface and perimeter sites and play the role of “stoves” that burn ethanol molecules and their partially oxidized derivatives to the “final” products. The ?-Al2O3 surfaces provided higher mobility of the fragments of ethanol molecules than the SiO2 surface and hence increased the supply rate of these objects to the Pt particles. This will in turn produce a higher conversion rate of unburned ethanol.

This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

Methods and systems for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbonmonoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbonmonoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

Methods and systems are disclosed for treating vapors from fuels such as gasoline or diesel fuel in an internal combustion engine, to form hydrogen gas or synthesis gas, which can then be burned in the engine to produce more power. Fuel vapor, or a mixture of fuel vapor and exhaust gas and/or air, is contacted with a plasma, to promote reforming reactions between the fuel vapor and exhaust gas to produce carbonmonoxide and hydrogen gas, partial oxidation reactions between the fuel vapor and air to produce carbonmonoxide and hydrogen gas, or direct hydrogen and carbon particle production from the fuel vapor. The plasma can be a thermal plasma or a non-thermal plasma. The plasma can be produced in a plasma generating device which can be preheated by contact with at least a portion of the hot exhaust gas stream, thereby decreasing the power requirements of the plasma generating device.

Nano-sized lithium manganese oxide (LMO) dispersed on carbon nanotubes (CNT) has been synthesized successfully via a microwave-assisted hydrothermal reaction at 200 C for 30 min using MnO{sub 2}-coated CNT and an aqueous LiOH solution. The initial specific capacity is 99.4 mAh/g at a 1.6 C-rate, and is maintained at 99.1 mAh/g even at a 16 C-rate. The initial specific capacity is also maintained up to the 50th cycle to give 97% capacity retention. The LMO/CNT nanocomposite shows excellent power performance and good structural reversibility as an electrode material in energy storage systems, such as lithium-ion batteries and electrochemical capacitors. This synthetic strategy opens a new avenue for the effective and facile synthesis of lithium transition metal oxide/CNT nanocomposite.

Polyhalide ions (Br-/BrCl2-) are an important redox couple for redox flow batteries. The oxidation-reduction behavior of polyhalide ions on a carbon nanotube (CNT) electrode has been investigated with cyclic voltammetry and electrochemical impedance spectroscopy. The onset oxidation potential of Br-/BrCl2- is negatively shifted by >100 mV, and the redox current peaks are greatly enhanced on a CNT electrode compared with that on the most widely-used graphite electrode. The reaction resistance of the redox couple (Br-/BrCl2-) is decreased on a CNT electrode. The redox reversibility is increased on a CNT electrode even though it still needs further improvement. CNT is a promising electrode material for redox flow batteries.

This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

Remediation and long-term stewardship of uranium-contaminated sediments and groundwaters are critical problems at a number of DOE facilities and mining sites. Some remediation strategies based on in-situ bioreduction of U are potentially effective in significantly decreasing U concentrations in groundwaters. However, a number of basic processes require understanding in order to identify conditions more conducive to success of reduction-based U stabilization. Our current research targets several of these issues including: (1) effects of organic carbon (OC) forms and supply rates on stability of bioreduced U, (2) the roles of Fe(III)- and Mn(III,IV)-oxides as potential U oxidants in sediments, and (3) microbial community changes in relation to U redox changes. These issues were identified in our previous study on U bioreduction and reoxidation (Wan et al., 2005). Most of our studies are being conducted on historically U-contaminated sediments from Area 2 of the Field Research Center, Oak Ridge National Laboratory, in flow-through columns simulating in-situ field remediation.

of the structure in oxygen rich environments in excess of 450 OC. A common protection scheme includes the use of external oxidation barrier coatings in conjunction with internal particulate oxidation inhibitors. The goal of this research is to gain...

The structural analysis of carbon-carbon (C-C) composites is a research area of increasing importance. As the use of the materials expands towards more demanding aerospace applications, it is of critical importance to understand the laminate...

The fixation of inorganic carbon (as carbon dioxide) has been documented in all three domains of life and results in the biosynthesis of a diverse suite of organic compounds that support the growth of heterotrophic organisms. The primary aim of this study was to assess the importance of carbon dioxide fixation in high-temperature Fe(III)-oxide mat communities and in pure cultures of one of the dominant Fe(II)-oxidizing organisms (Metallosphaera yellowstonensis strain MK1) present in situ. Protein-encoding genes of the complete 3-hydroxypropionate/4-hydroxybutyrate (3-HP/4-HB) carbon fixation pathway were identified in pure-cultures of M. yellowstonensis strain MK1. Metagenome sequencing from the same environments also revealed genes for the 3-HP/4-HB pathway belonging to M. yellowstonensis populations, as well as genes for a complete reductive TCA cycle from Hydrogenobaculum spp. (Aquificales). Stable isotope (13CO2) labeling was used to measure the fixation of CO2 by M. yellowstonensis strain MK1, and in ex situ assays containing live Fe(III)-oxide microbial mats. Results showed that M. yellowstonensis strain MK1 fixes CO2 via the 3-HP/4-HB pathway with a fractionation factor of ~ 2.5 ‰. Direct analysis of the 13C composition of dissolved inorganic C (DIC), dissolved organic C (DOC), landscape C and microbial mat C showed that mat C is comprised of both DIC and non-DIC sources. The estimated contribution of DIC carbon to biomass C (> ~ 35%) is reasonably consistent with the relative abundance of known chemolithoautotrophs and corresponding CO2 fixation pathways detected in metagenome sequence. The significance of DIC as a major source of carbon for Fe-oxide mat communities provides a foundation for examining microbial interactions in these systems that are dependent on the activity of autotrophic organisms such as Hydrogenobaculum and Metallosphaera spp.

High-performance p-type carbon nanotube (CNT) transistors utilizing yttrium oxide as gate dielectric are presented by optimizing oxidization and annealing processes. Complementary metal-oxide-semiconductor (CMOS) field-effect-transistors (FETs) are then fabricated on CNTs, and the p- and n-type devices exhibit symmetrical high performances, especially with low threshold voltage near to zero. The corresponding CMOS CNT inverter is demonstrated to operate at an ultra-low supply voltage down to 0.2?V, while displaying sufficient voltage gain, high noise margin, and low power consumption. Yttrium oxide is proven to be a competitive gate dielectric for constructing high-performance CNT CMOS FETs and integrated circuits.

in conventional carbon based jet fuel systems. The combustion of hydrocarbon based fuels can reach temperatures monoxide (11 BO; X2 + ) radical with unsaturated hydrocarbons are of importance in understanding the formation of small boron-oxygen bearing hydrocarbons in boron combustion processes. Over recent decades

'The background for the project is briefly reviewed and the work done during the nine months since funding was received is documented. Work began in January, 1997. A post doctoral fellow joined the team in April. The major activities completed this fiscal year were: staffing the project, design of the experimental system, procurement of components, assembly of the system. preparation of the Safe Operating Procedure and ES and H compliance, pressure testing, establishing data collection and storage methodology, and catalyst preparation. Objective The objective of the project is to develop new chemistry for the removal of organic contaminants from supercritical carbon dioxide. This has application in processes used for continuous cleaning and extraction of parts and waste materials. A secondary objective is to increase the fundamental understanding of photocatalytic chemistry. Cleaning and extraction using supercritical carbon dioxide (scCO{sub 2}) can be applied to the solution of a wide range of environmental and pollution prevention problems in the DOE complex. Work is being done that explores scCO{sub 2} in applications ranging from cleaning contaminated soil to cleaning components constructed from plutonium. The rationale for use of scCO{sub 2} are based on the benign nature, availability and low cost, attractive solvent properties, and energy efficient separation of the extracted solute from the solvent by moderate temperature or pressure changes. To date, R and D has focussed on the methods and applications of the extraction steps of the process. Little has been done that addresses methods to polish the scCO{sub 2} for recycle in the cleaning or extraction operations. In many applications it will be desirable to reduce the level of contamination from that which would occur at steady state operation of a process. This proposal addresses chemistry to achieve that. This would be an alternative to removing a fraction of the contaminated scCO{sub 2} for disposal and using makeup scCO{sub 2}. A chemical polishing operation can reduce the release of CO{sub 2} from the process. It can also reduce the consumption of reagents that may be used in the process to enhance extraction and cleaning. A polishing operation will also reduce or avoid formation of an additional waste stream. Photocatalytic and other photochemical oxidation chemistry have not been investigated in scCO{sub 2}. The large base of information for these reactions in water, organic solvents, or air suggest that the chemistry will work in carbon dioxide. There are compelling reasons to believe that the properties of scCO{sub 2} should increase the performance of photocatalytic chemistry over that found in more conventional fluid phases.'

This final report covers work done during project period one and project period two. All the work in project period one was focused on the selective oxidation of oxygenated hydrocarbons over the SnO{sub 2}(110) single crystal surface. In project period two, the emphasis was on the acid/base properties of SnO{sub 2}(110) as well as two different Cu{sub 2}O single crystal surfaces. Prior to the summary of results, a description of these different surfaces is given as background information. Results are described for the dissociation and reaction of Bronsted acids (methanol, formic acid, water, formaldehyde, acetone, propene, acetic acid, and carbonmonoxide). Results from project period two include: ammonia adsorption, CO{sub 2} adsorption, propene adsorption and oxidation, with tin oxides; complimentary work with copper oxides; and STM investigations.

Thin amorphous manganese oxide layers with a thickness of 3-5nm are electrodeposited on a carbon nanotube (CNT) film substrate that has a three-dimensional nanoporous structure (denoted asMnO2/CNT electrode). For the purpose of comparison, manganese oxide films are also electrodeposited on a flat Pt-coated Si wafer substrate (denoted as MnO2 film electrode). The pseudocapacitive properties of the MnO2 film and MnO2/CNT electrodes are examined in both aqueous electrolyte (1.0M KCl) and nonaqueousorganic electrolyte (1.0M LiClO4 in propylene carbonate). While both types of electrode showpseudocapacitive behaviour in the aqueous electrolyte, only the MnO2/CNT electrode does so in the organic electrolyte, due to its high oxide/electrolyte interfacial area and improved electron conduction through the CNT substrate. Compared with the MnO2 film electrode, the MnO2/CNT electrode shows a much higher specific capacitance and better high-rate capability, regardless of the electrolyte used.Use of the organic electrolyte results in a ?6 times higher specific energy compared with that obtained with the aqueous electrolyte, while maintaining a similar specific power. The construction of a threedimensional nanoporous network structure consisting of a thin oxide layer on a CNT film substrate at the nm scale and the use of an organic electrolyte are promising approaches to improving the specific energyof supercapacitors.

A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust.

Monodisperse palladium particles of six distinct and controlled sizes between 4-16 nm were synthesized in a one-pot polyol process by varying the molar ratios of the two palladium precursors used, which contained palladium in different oxidation states. This difference permitted size control by regulation of the nucleation rate because low oxidation state metals ions nucleate quickly relative to high oxidation state ions. After immobilization of the Pd particles on silica by mild sonication, the catalysts were characterized by X-ray absorption spectroscopy and applied toward catalytic methanol decomposition. This reaction was determined as structure sensitive with the intrinsic activity (turnover frequency) increasing with increasing particle size. Moreover, observed catalytic deactivation was linked to product (carbonmonoxide) poisoning. Co-feeding carbon dioxide caused the activity and the amount of deactivation to decrease substantially. A reaction mechanism based on the formation of the {pi}-bond between carbon and oxygen as the rate-limiting step is in agreement with antipathetic structure sensitivity and product poisoning by carbonmonoxide.

Nanoporous composites of carbon nanosheets (CNS) and titania nanoparticles (NPs) were synthesized by reassembling of delaminated graphite oxide (GO) layers with titania clear sol (TCS), and their structural and porous properties were examined by various physico-chemical methods such as XRD, TG/DTA, FT-IR, Raman, FE-SEM/TEM, and low temperature N{sub 2} adsorption. It was found that the facile approach, which utilizes the electrostatic attraction between the negatively charged GO layers and the positively charged TCS particles, leads to a well composed CNS and ultrafine TiO{sub 2} NPs material whose titania amount reaches up to 71 wt%. The titania phase in these composite materials is mainly anatase, which is resistible against high temperature calcination, but also contains a little amount of rutile and brookite depending on synthesis condition. The porosity of the composite is improved and partially affected by the size distributions of TiO{sub 2} NPs. The unique structure, better porosity, and compatible surface affinity of these composites bring about an adsorption concentration-promoted photocatalytic effects toward organic dyes by successfully combining both properties of CNS and titania NPs. - Graphical Abstract: Carbon nanosheet-titania nanocrystal composites can be synthesized by a facile delamination-reassembling method from graphene oxide and colloidal titania. Highlights: Black-Right-Pointing-Pointer A facile delamination-reassembling method for graphene oxide-titania nanocomposite. Black-Right-Pointing-Pointer A nanoporous composite containing mixed phase titania nanocrystals. Black-Right-Pointing-Pointer Partition effect of carbon nanosheets preventing TiO{sub 2} nanoparticles from aggregating. Black-Right-Pointing-Pointer Adsorption concentration-promoted photocatalysis.

We show that the modification of a gold/carbon catalyst with Pt or Pd produces stable and recyclable catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). This finding is a significant advance over current conversion technology because of the technological importance of FDCA. Indeed, FDCA has been identified as one of twelve potential building blocks for the production of value added chemicals derived from biosources.1 FDCA is a potential replacement source of terephthalic acid, the monomer presently used for the production of polyethylene terephthalate (PET) and derived from hydrocarbon sources.2

Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g{sup ?1} Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superior to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup ?1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup ?1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.

A process for converting potassium sulfate to potassium carbonate in which a mixture of potassium sulfate and calcium oxide are reacted at a temperature in the range of between about 700.degree. C. and about 800.degree. C. with a gaseous mixture having a minor amount of hydrogen and/or carbonmonoxide in a diluent with the calcium oxide being present in an amount not greater than about 20 percent by weight of the potassium sulfate to produce an aqueous mixture of potassium sulfide, potassium bisulfide, potassium hydroxide and calcium sulfide and a gaseous mixture of steam and hydrogen sulfide. The potassium and calcium salts are quenched to produce an aqueous slurry of soluble potassium salts and insoluble calcium salts and a gaseous mixture of steam and hydrogen sulfide. The insoluble calcium salts are then separated from the aqueous solution of soluble potassium salts. The calcium salts are dried to produce calcium sulfide, calcium bisulfide and steam, and then, the calcium sulfide and calcium bisulfide are converted to the oxide and recycled. The soluble potassium salts are carbonated to produce potassium carbonate which is concentrated and the precipitated crystals separated. The sulfur-containing compounds are further treated.

ABSTRACT Since Direct Carbon Fuel Cell (DCFC) technology is in a beginning stage, emphasis should be laid on addressing the fundamental aspects. A molten electrolyte is required to facilitate ionic contact between solid ...

- ronmental impact. Present technology uses steam reforming to produce synthesis gas which is converted into enhance- ment of the carbon balance of methane conversion by reforming with CO2 in order to "recycle

The effects of temperature and acidic pretreatment on Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC, derived from bituminous coal) were investigated. Limiting factors in MTBE removal in GAC include the heterogeneous distribution of amended Fe, and slow intraparticle diffusive transport of MTBE and hydrogen peroxide (H{sub 2}O{sub 2}) into the 'reactive zone'. Acid pretreatment of GAC before Fe amendment altered the surface chemistry of the GAC, lowered the pH point of zero charge, and resulted in greater penetration and more uniform distribution of Fe in GAC. This led to a condition where Fe, MTBE, and H{sub 2}O{sub 2} coexisted over a larger volume of the GAC contributing to greater MTBE oxidation and removal. H{sub 2}O{sub 2} reaction and MTBE removal in GAC increased with temperature. Modeling H{sub 2}O{sub 2} transport and reaction in GAC indicated that H{sub 2}O{sub 2} penetration was inversely proportional with temperature and tortuosity, and occurred over a larger fraction of the total volume of small GAC particles (0.3 mm diameter) relative to large particles (1.2 mm diameter). Acidic pretreatment of GAC, Fe-amendment, elevated reaction temperature, and use of small GAC particles are operational parameters that improve Fenton-driven oxidation of MTBE in GAC. 29 refs., 6 figs., 1 tab.

The solubility of CO in 1,4-dioxane was determined as a function of pressure (7-70 atm) and temperature (80-173/sup 0/C). An expression is given for solubility that relates the mole fraction and partial pressure of CO (in atmospheres) and the temperature in degrees Kelvin. The results, analyzed in terms of the Krichevsky-Ilinskaya equation, showed that the partial molar volume of CO was independent of pressure and that the isobaric Henry's law was obeyed in the ranges studied. Comparisons with other solvents showed that, on the basis of CO dissolution characteristics, 1,4-dioxane can be classified better with polar than with nonpolar solvents.

November), biomass burning in the southern tropics produces large-scale plumes of CO. These plumes can biomass-burning regions generally rises into the middle and upper troposphere, where it is entrained. For example, it is now clear that the main population areas in the northern hemisphere (North America, Europe

We report spectroscopic and imaging observations of rotational transitions of cold CO and SiO in the ejecta of SN1987A, the first such emission detected in a supernova remnant. In addition to line luminosities for the CO J = 1-0, 2-1, 6-5, and 7-6 transitions, we present upper limits for all other transitions up to J = 13-12, collectively measured from the Atacama Large Millimeter Array, the Atacama Pathfinder EXperiment, and the Herschel Spectral and Photometric Imaging REceiver. Simple models show the lines are emitted from at least 0.01 M{sub Sun} of CO at a temperature >14 K, confined within at most 35% of a spherical volume expanding at {approx}2000 km s{sup -1}. Moreover, we locate the emission within 1'' of the central debris. These observations, along with a partial observation of SiO, confirm the presence of cold molecular gas within supernova remnants and provide insight into the physical conditions and chemical processes in the ejecta. Furthermore, we demonstrate the powerful new window into supernova ejecta offered by submillimeter observations.

of greenhouse gases such as CH4 and O3. Consequently, CO has an atmospheric lifetime of 1-3 months, making it a good tracer for studying the long range transport of pollution. Satellite observations present a valuable tool to investigate tropospheric CO...

The present invention is a process for the carbothermic reduction of silicon dioxide to form elemental silicon. Carbon balance of the process is assessed by measuring the amount of carbonmonoxide evolved in offgas exiting the furnace. A ratio of the amount of carbonmonoxide evolved and the amount of silicon dioxide added to the furnace is determined. Based on this ratio, the carbon balance of the furnace can be determined and carbon feed can be adjusted to maintain the furnace in carbon balance.

is attributed to the formation of a hydrogen-bonded nanotube network. The oxidized tubes bind readily to amine been demonstrated. They have been successfully used in nanoelectronic2 and photovoltaic3 devices and as scanning probe tips,9 chemical10a and flow10b sensors, hydrogen-storage reservoirs,11 nanocomposite

applications. A vacuum-assisted, in situ electrodeposition process has been used to achieve the three-dimensional functionalization of CNT forests with inserted nickel nanoparticles as pseudocapacitor electrodes. Experimental CNT forest samples, and the oxidized nickel nanoparticle/CNT supercapacitor retained 94.2% of its

Lignin is an underused but major component of biomass. One possible area of utilization is the production of carbon fiber. A necessary processing step is the stabilization of lignin fiber (typically in an oxygen environment) before high temperature treatment. We investigate oxidative, thermal conversion of lignin using computational methods. Dilignol model compounds for the most common (seven) linkages in softwood are chosen to represent the diverse structure of lignin. We perform molecular dynamics simulation where the potential energy surface is described by a reactive force field (ReaxFF). We calculate overall activation energies for model conversion and reveal initial mechanisms of formaldehyde formation. We record fragmentation patterns and average carbonoxidation numbers at various temperatures. Most importantly, we identify mechanisms for stabilizing reactions that result in cyclic, and rigid connections in softwood lignin fibers that are necessary for further processing into carbon fibers.

is endothermic with activation energy of 80kJ mol-1 [16], which means that the coke cools down during the reaction therefore energy is constantly supplied during the reaction to keep the coal hot. It is thought that the amounts of the carbonmonoxide... ??? (1) In industry, water is blown through hot coke and the resulting gas is called water gas, which is a mixture of hydrogen (H2, 50%), carbonmonoxide (CO, 40%), carbon dioxide (CO2, 5%), nitrogen and methane (N2 + CH4, 5%). This reaction...

Method for producing carbon nanotubes. Carbon nanotubes were prepared using a low power, atmospheric pressure, microwave-generated plasma torch system. After generating carbonmonoxide microwave plasma, a flow of carbonmonoxide was directed first through a bed of metal particles/glass beads and then along the outer surface of a ceramic tube located in the plasma. As a flow of argon was introduced into the plasma through the ceramic tube, ropes of entangled carbon nanotubes, attached to the surface of the tube, were produced. Of these, longer ropes formed on the surface portion of the tube located in the center of the plasma. Transmission electron micrographs of individual nanotubes revealed that many were single-walled.

Arthur D. Little in conjunction with the Department of Energy and the Illinois Department of Commerce and Community Affairs are developing an ethanol fuel processor for fuel cell vehicles. Initial studies were carried out on a 25 kWe catalytic partial oxidation (POX) reformer to determine the effect of equivalence ratio, steam to carbon ratio, and residence time on ethanol conversion. Results of the POX experiments show near equilibrium yields of hydrogen and carbonmonoxide for an equivalence ratio of 3.0 with a fuel processor efficiency of 80%. The size and weight of the prototype reformer yield power densities of 1.44 l/kW and 1.74 kg/kW at an estimated cost of $20/kW.

and applications is dihydrogen or molecular hydrogen. Both the Heber process, in which nitrogen is converted to ammonia on an iron catalyst, and the Fischer-Tropsch synthesis, in which carbonmonoxide is converted to hydrocarbons over iron and cobalt catalysts... systems containing hydride ligands. This work presents a computational method for examining the energetics and structures of two systems. The reaction RhC1(CO)(PHs)z + Hz ~ (H)zRhC1(CO)(PHs)z was examined to a~plain why the oxidation of RhCI(CO...

In real life applications, supercapacitors (SCs) often can only be used as part of a hybrid system together with other high energy storage devices due to their relatively lower energy density in comparison to other types of energy storage devices such as batteries and fuel cells. Increasing the energy density of SCs will have a huge impact on the development of future energy storage devices by broadening the area of application for SCs. Here, we report a simple and scalable way of preparing a three-dimensional (3D) sub-5 nm hydrous ruthenium oxide (RuO?) anchored graphene and CNT hybrid foam (RGM) architecture for high-performance supercapacitor electrodes. This RGM architecture demonstrates a novel graphene foam conformally covered with hybrid networks of RuO? nanoparticles and anchored CNTs. SCs based on RGM show superior gravimetric and per-area capacitive performance (specific capacitance: 502.78 F g?¹, areal capacitance: 1.11 F cm?²) which leads to an exceptionally high energy density of 39.28 Wh kg?¹ and power density of 128.01 kW kg?¹. The electrochemical stability, excellent capacitive performance, and the ease of preparation suggest this RGM system is promising for future energy storage applications.

This paper investigates the feasibility of extracting and separating uranium from lanthanides and other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of a counter current stripping technique, which would be a more efficient and environmentally benign technology for spent nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U, Pu, and Np) and europium were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, uranium/europium and uranium/plutonium extraction and separation in sc-CO2 modified with TBP is successful at nitric acid concentrations of less than 6 M and at nitric acid concentrations of less than 3 M with acetohydroxamic acid or oxalic acid, respectively. A scheme for recycling uranium from spent nuclear fuel by using sc-CO2 and counter current stripping columns is presented.

This paper investigates the feasibility of extracting and separating uranium from lanthanides and other actinides by using supercritical fluid carbon dioxide (sc-CO{sub 2}) as a solvent modified with tri-n-butylphosphate (TBP) for the development of a counter current stripping technique, which would be a more efficient and environmentally benign technology for spent nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U, Pu, and Np) and europium were extracted in sc-CO{sub 2} modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, uranium/europium and uranium/plutonium extraction and separation in sc-CO{sub 2} modified with TBP is successful at nitric acid concentrations of less than 6 M and at nitric acid concentrations of less than 3 M with acetohydroxamic acid or oxalic acid, respectively. A scheme for recycling uranium from spent nuclear fuel by using sc-CO{sub 2} and counter current stripping columns is presented. (authors)

depending on the ratio of hydrogen to carbonmonoxide. Most synthesis gas is produced by the steam reform reaction. Industrially, steam reforming is performed over a Ni/ Al2O3 catalyst.9 The typical problem

The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbonmonoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

Splitting the C-C bond is the main obstacle to electroxidation of ethanol (EOR) to CO2. We recently demonstrated that the ternary PtRhSnO2 electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We synthesized, characterized and compared the properties of several ternary electrocatalysts. Carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO2 NP core decorated with multi-metallic nanoislands (MM = PtIr, PtRh, IrRh, PtIrRh) were prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM /SnO2 NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity towards CO2 formation of several of these MM /SnO2/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO2/C catalysts. We demonstrate that the PtIr/SnO2/C catalyst with high Ir content shows outstanding catalytic property with the most negative EOR onset potential and reasonably good selectivity towards ethanol complete oxidation to CO2. PtRh/SnO2/C catalysts with a moderate Rh content exhibit the highest EOR selectivity, as deduced from infrared studies.

A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust. Carbon aerogels can be coated with sol-gel silica and the silica can be converted to silicone carbide, improved the thermal stability of the carbon aerogel.

Single-wall carbon nanotubes (SWCNTs) are very important materials due to their combination of unique structure, dimension, strength, chemical stability, and electronic properties. Nevertheless, SWCNTs from commercial sources usually contain several impurities, which are usually removed by a purification process that includes reflux in acids and strong oxidation. This strong chemical procedure may alter the nanotube properties and it is thus important to control the extent of functionalization and oxidation during the purification procedure. In this report, we provide a comprehensive study of the structure and physical composition of SWCNTs during each step of the purification process. Techniques such as Raman spectroscopy, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy and Infrared spectroscopy were used to track the SWCNTs structure, in terms of length and diameter distribution, and surface chemical modifications during each purification stage.

A high temperature solid oxide fuel cell generator produces electrical power from oxidation of hydrocarbon fuel gases such as natural gas, or conditioned fuel gases, such as carbonmonoxide or hydrogen, with oxidant gases, such as air or oxygen. This electrochemical reaction occurs in a plurality of electrically connected solid oxide fuel cells bundled and arrayed in a unitary modular fuel cell stack disposed in a compartment in the generator container. The use of a unitary modular fuel cell stack in a generator is similar in concept to that of a removable battery. The fuel cell stack is provided in a pre-assembled self-supporting configuration where the fuel cells are mounted to a common structural base having surrounding side walls defining a chamber. Associated generator equipment may also be mounted to the fuel cell stack configuration to be integral therewith, such as a fuel and oxidant supply and distribution systems, fuel reformation systems, fuel cell support systems, combustion, exhaust and spent fuel recirculation systems, and the like. The pre-assembled self-supporting fuel cell stack arrangement allows for easier assembly, installation, maintenance, better structural support and longer life of the fuel cells contained in the fuel cell stack. 8 figs.

A high temperature solid oxide fuel cell generator produces electrical power from oxidation of hydrocarbon fuel gases such as natural gas, or conditioned fuel gases, such as carbonmonoxide or hydrogen, with oxidant gases, such as air or oxygen. This electrochemical reaction occurs in a plurality of electrically connected solid oxide fuel cells bundled and arrayed in a unitary modular fuel cell stack disposed in a compartment in the generator container. The use of a unitary modular fuel cell stack in a generator is similar in concept to that of a removable battery. The fuel cell stack is provided in a pre-assembled self-supporting configuration where the fuel cells are mounted to a common structural base having surrounding side walls defining a chamber. Associated generator equipment may also be mounted to the fuel cell stack configuration to be integral therewith, such as a fuel and oxidant supply and distribution systems, fuel reformation systems, fuel cell support systems, combustion, exhaust and spent fuel recirculation systems, and the like. The pre-assembled self-supporting fuel cell stack arrangement allows for easier assembly, installation, maintenance, better structural support and longer life of the fuel cells contained in the fuel cell stack.

A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbonmonoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

This paper presents the emissions testing results of various heavy duty engines and vehicles with and without retrofitted diesel oxidation catalyst technology. 1987 Cummins L10 and 1991 DDC 6V92TA DDECII engine results over the US Heavy Duty Transient Test are presented for comparison to chassis test results. The vehicles in this study include two urban buses, two school buses and three heavy duty trucks. The Central Business District, New York Bus and New York Composite urban driving cycles have been used to evaluate baseline emissions and the catalyst performance on a heavy duty chassis dynamometer. The results demonstrate that 25--45% particulate reduction is readily achievable on a wide variety of heavy duty vehicles. Significant carbonmonoxide and hydrocarbon reductions were also observed.

A method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide within a reformer 10 is disclosed. According to the method, a stream including an oxygen-containing gas is directed adjacent to a first vessel 18 and the oxygen-containing gas is heated. A stream including unburned fuel is introduced into the oxygen-containing gas stream to form a mixture including oxygen-containing gas and fuel. The mixture of oxygen-containing gas and unburned fuel is directed tangentially into a partial oxidation reaction zone 24 within the first vessel 18. The mixture of oxygen-containing gas and fuel is further directed through the partial oxidation reaction zone 24 to produce a heated reformate stream including hydrogen gas and carbonmonoxide. Steam may also be mixed with the oxygen-containing gas and fuel, and the reformate stream from the partial oxidation reaction zone 24 directed into a steam reforming zone 26. High- and low-temperature shift reaction zones 64,76 may be employed for further fuel processing.

Deforestation in Brazilian Amazonia in 1990 was releasing approximately 281--282 X 10{sup 6} metric tons (MT) of carbon on conversion to a landscape of agriculture, productive pasture, degraded pasture, secondary forest and regenerated forest in the proportions corresponding to the equilibrium condition implied by current land-use patterns. Emissions are expressed as committed carbon,'' or the carbon released over a period of years as the carbon stock in each hectare deforested approaches a new equilibrium in the landscape that replaces the original forest. To the extent that deforestation rates have remained constant, current releases from the areas deforested in previous years will be equal to the future releases from the areas being cleared now. Considering the quantities of carbon dioxide, carbonmonoxide, methane, nitrous oxide, NO{sub x} and non-methane hydrocarbons released raises the impact by 22--37%. The relative impact on the greenhouse effect of each gas is based on the Intergovernmental Panel on Climate Change (IPCC) calculations over a 20-year time period (including indirect effects). The six gases considered have a combined global warming impact equivalent to 343 to 386 million MT of C0{sub 2}-equivalent carbon, depending on assumptions regarding the release of methane and other gases from the various sources such as burning and termites. These emissions represent 7--8 times the 50 million MT annual carbon release from Brazil's use of fossil fuels, but bring little benefit to the country. Stopping deforestation in Brazil would prevent as much greenhouse emission as tripling the fuel efficiency of all the automobiles in the world. The relatively cheap measures needed to contain deforestation, together with the many complementary benefits of doing so, make this the first priority for funds intended to slow global warming.

Fracture resistant silicon carbide ceramics are provided by incorporating therein a particulate dispersoid selected from the group consisting of (a) a mixture of boron, carbon and tungsten, (b) a mixture of boron, carbon and molybdenum, (c) a mixture of boron, carbon and titanium carbide, (d) a mixture of aluminum oxide and zirconium oxide, and (e) boron nitride. 4 figures.

The National Risk Assessment Partnership (NRAP) consists of 5 U.S DOE national laboratories collaborating to develop a framework for predicting the risks associated with carbon sequestration. The approach taken by NRAP is to divide the system into components, including injection target reservoirs, wellbores, natural pathways including faults and fractures, groundwater and the atmosphere. Next, develop a detailed, physics and chemistry-based model of each component. Using the results of the detailed models, develop efficient, simplified models, termed reduced order models (ROM) for each component. Finally, integrate the component ROMs into a system model that calculates risk profiles for the site. This report details the development of the Groundwater Geochemistry ROM for the Edwards Aquifer at PNNL. The Groundwater Geochemistry ROM for the Edwards Aquifer uses a Wellbore Leakage ROM developed at LANL as input. The detailed model, using the STOMP simulator, covers a 5x8 km area of the Edwards Aquifer near San Antonio, Texas. The model includes heterogeneous hydraulic properties, and equilibrium, kinetic and sorption reactions between groundwater, leaked CO2 gas, brine, and the aquifer carbonate and clay minerals. Latin Hypercube sampling was used to generate 1024 samples of input parameters. For each of these input samples, the STOMP simulator was used to predict the flux of CO2 to the atmosphere, and the volume, length and width of the aquifer where pH was less than the MCL standard, and TDS, arsenic, cadmium and lead exceeded MCL standards. In order to decouple the Wellbore Leakage ROM from the Groundwater Geochemistry ROM, the response surface was transformed to replace Wellbore Leakage ROM input parameters with instantaneous and cumulative CO2 and brine leakage rates. The most sensitive parameters proved to be the CO2 and brine leakage rates from the well, with equilibrium coefficients for calcite and dolomite, as well as the number of illite and kaolinite sorption sites proving to be of secondary importance. The Groundwater Geochemistry ROM was developed using nonlinear regression to fit the response surface with a quadratic polynomial. The goodness of fit was excellent for the CO2 flux to the atmosphere, and very good for predicting the volumes of groundwater exceeding the pH, TDS, As, Cd and Pb threshold values.

The present invention provides novel catalysts for accomplishing catalytic decomposition of undiluted light hydrocarbons to a hydrogen product, and methods for preparing such catalysts. In one aspect, a method is provided for preparing a catalyst by admixing an aqueous solution of an iron salt, at least one additional catalyst metal salt, and a suitable oxide substrate support, and precipitating metal oxyhydroxides onto the substrate support. An incipient wetness method, comprising addition of aqueous solutions of metal salts to a dry oxide substrate support, extruding the resulting paste to pellet form, and calcining the pellets in air is also discloses. In yet another aspect, a process is provided for producing hydrogen from an undiluted light hydrocarbon reactant, comprising contacting the hydrocarbon reactant with a catalyst as described above in a reactor, and recovering a substantially carbonmonoxide-free hydrogen product stream. In still yet another aspect, a process is provided for catalytic decomposition of an undiluted light hydrocarbon reactant to obtain hydrogen and a valuable multi-walled carbon nanotube coproduct.

A hydrogen permeable membrane, which includes a polymer stable at temperatures of about 200 C having clay impregnated with Pt or Au or Ru or Pd particles or mixtures thereof with average diameters of less than about 10 nanometers (nms) is disclosed. The membranes are useful in fuel cells or any device which requires hydrogen to be separated from carbonmonoxide.

Reactivity Controlled Compression Ignition (RCCI) has been shown to allow for diesel-like or better brake thermal efficiency with significant reductions in nitrogen oxide (NOX) particulate matter (PM) emissions. Hydrocarbon (HC) and carbonmonoxide (CO) emission levels, on the other hand, are similar to those of port fuel injected gasoline engines. The higher HC and CO emissions combined with the lower exhaust temperatures with RCCI operation present a challenge for current exhaust aftertreatments. The reduction of HC and CO emissions in a lean environment is typically achieved with an oxidation catalyst. In this work, several diesel oxidation catalysts (DOC) with different precious metal loadings were evaluated for effectiveness to control HC and CO emissions from RCCI combustion in a light-duty multi-cylinder engine operating on gasoline and diesel fuels. Each catalyst was evaluated in a steady-state engine operation with temperatures ranging from 160 to 260 C. A shift to a higher light-off temperature was observed during the RCCI operation. In addition to the steady-state experiments, the performances of the DOCs were evaluated during multi-mode engine operation by switching from diesel-like combustion at higher exhaust temperature and low HC/CO emissions to RCCI combustion at lower temperature and higher HC/CO emissions. High CO and HC emissions from RCCI generated an exotherm keeping the catalyst above the light-off temperature.

) in extraterrestrial, low temperature ices. Reactants and products were analyzed on line and in situ via absorption with a 1/r2 dependence, r being the distance from the sun, and thus becomes less important when the outer% H+ , 2% He2+ , and few heavier nuclei; the energy distribution maximum peaks at around 10 MeV where

A new ironmaking concept is being proposed that involves the combination of a rotary hearth furnace (RHF) with an iron-bath smelter. The RHF makes use of iron-oxide-carbon composite pellets as the charge material and the final product is direct-reduced iron (DRI) in the solid or molten state. This part of the research includes the development of a reactor that simulated the heat transfer in an RHF. The external heat-transport and high heating rates were simulated by means of infrared (IR) emitting lamps. The reaction rates were measured by analyzing the off-gas and computing both the amount of CO and CO{sub 2} generated and the degree of reduction. The reduction times were found to be comparable to the residence times observed in industrial RHFs. Both artificial ferric oxide (PAH) and naturally occurring hematite and taconite ores were used as the sources of iron oxide. Coal char and devolatilized wood charcoal were the reductants. Wood charcoal appeared to be a faster reductant than coal char. However, in the PAH-containing pellets, the reverse was found to be true because of heat-transfer limitations. For the same type of reductant, hematite-containing pellets were observed to reduce faster than taconite-containing pellets because of the development of internal porosity due to cracking and fissure formation during the Fe2O{sub 3}-to-Fe3O{sub 4} transition. This is, however, absent during the reduction of taconite, which is primarily Fe3O{sub 4}. The PAH-wood-charcoal pellets were found to undergo a significant amount of swelling at low-temperature conditions, which impeded the external heat transport to the lower layers. If the average degree of reduction targeted in an RHF is reduced from 95 to approximately 70 pct by coupling the RHF with a bath smelter, the productivity of the RHF can be enhanced 1.5 to 2 times. The use of a two- or three-layer bed was found to be superior to that of a single layer, for higher productivities.

A number of materials with the composition Li.sub.1+xNi.sub..alpha.Mn.sub..beta.Co.sub..gamma.M'.sub..delta.O.sub.2-- zF.sub.z (M'=Mg,Zn,Al,Ga,B,Zr,Ti) for use with rechargeable batteries, wherein x is between about 0 and 0.3, .alpha. is between about 0.2 and 0.6, .beta. is between about 0.2 and 0.6, .gamma. is between about 0 and 0.3, .delta. is between about 0 and 0.15, and z is between about 0 and 0.2. Adding the above metal and fluorine dopants affects capacity, impedance, and stability of the layered oxide structure during electrochemical cycling. Another aspect of the invention includes materials with the composition Li.sub.1+xNi.sub..alpha.Co.sub..beta.Mn.sub..gamma.M'.sub..delta.O.sub.yF- .sub.z (M'=Mg,Zn,Al,Ga,B,Zr,Ti), where the x is between 0 and 0.2, the .alpha. between 0 and 1, the .beta. between 0 and 1, the .gamma. between 0 and 2, the .delta. between about 0 and about 0.2, the y is between 2 and 4, and the z is between 0 and 0.5.

Large quantities of mixed low level waste (MLLW) that fall under the Toxic Substances Control Act (TSCA) exist and will continue to be generated during D and D operations at DOE sites across the country. The standard process for destruction of MLLW is incineration, which has an uncertain future. The extraction and destruction of PCBs from MLLW was the subject of this research Supercritical Fluid Extraction (SFE) with carbon dioxide with 5% ethanol as cosolvent and Supercritical Waster Oxidation (SCWO) were the processes studied in depth. The solid matrix for experimental extraction studies was Toxi-dry, a commonly used absorbent made from plant material. PCB surrogates were 1.2,4-trichlorobenzene (TCB) and 2-chlorobiphenyl (2CBP). Extraction pressures of 2,000 and 4,000 psi and temperatures of 40 and 80 C were studied. Higher extraction efficiencies were observed with cosolvent and at high temperature, but pressure little effect. SCWO treatment of the treatment of the PCB surrogates resulted in their destruction below detection limits.

The performance of Rh/ZnO/{gamma}-Al{sub 2}O{sub 3} catalyst for partial oxidation of methane to syngas was compared in fixed and fluidised bed reactors. Catalyst activity was found not to be a limiting factor under any experimental conditions and complete oxygen conversions were observed in all tests. In the fixed bed reactor both methane conversion and syngas selectivity were increasing with space velocity as the result of an autothermal effect. Satisfactory control of the catalyst temperature at high space velocities could only be achieved with addition of inert diluent or steam to the feed. Different conversion and selectivity patterns were observed in fluidised bed reactor. Methane conversion and carbonmonoxide selectivity were decreasing with increasing gas flow. By contrast, hydrogen selectivity showed distinct maximum at medium space velocities. These results are interpreted in terms of catalyst backmixing and its effect on primary and secondary reactions. Improved temperature control was also achieved in fluidised bed reactor. Several experiments using fluidised bed reactor were carried out at elevated pressures. To eliminate the occurrence of non-catalytic gas phase reactions between methane and oxygen very short feed mixing times (< 1 ms) were employed. Despite these measures the reactor could not be successfully operated at pressures above 0.7 MPa. The implications of these findings for process development are discussed.

Lean-burn engines offer the potential for significant fuel economy improvements in cars and trucks, perhaps the next great breakthrough in automotive technology that will enable greater savings in imported petroleum. The development of lean-burn engines, however, has been an elusive goal among automakers because of the emissions challenges associated with lead-burn engine technology. Presently, cars operate with sophisticated emissions control systems that require the engine's air-fuel ratio to be carefully controlled around the stoichiometric point (chemically correct mixture). Catalysts in these systems are called "three-way" catalysts because they can reduce hydrocarbon, carbonmonoxide, and nitrogen oxide emissions simultaneously, but only because of the tight control of the air-fuel ratio. The purpose of this cooperative effort is to develop advanced catalyst systems, materials, and necessary engine control algorithms for reducing NOX emissions in oxygen-rich automotive exhaust (as with lean-burn engine technology) to meet current and near-future mandated Clean Air Act standards. These developments will represent a breakthrough in both emission control technology and automobile efficiency. The total project is a joint effort among five national laboratories, together with US CAR. The role of Lockheed-Martin Energy Systems in the total project is two fold: characterization of catalyst performance through laboratory evaluations from bench-scale flow reactor tests to engine laboratory tests of full-scale prototype catalysts, and microstructural characterization of catalyst material before and after test stand and/or engine testing.

Deforestation in Brazilian Amazonia in 1990 was releasing approximately 281--282 X 10{sup 6} metric tons (MT) of carbon on conversion to a landscape of agriculture, productive pasture, degraded pasture, secondary forest and regenerated forest in the proportions corresponding to the equilibrium condition implied by current land-use patterns. Emissions are expressed as ``committed carbon,`` or the carbon released over a period of years as the carbon stock in each hectare deforested approaches a new equilibrium in the landscape that replaces the original forest. To the extent that deforestation rates have remained constant, current releases from the areas deforested in previous years will be equal to the future releases from the areas being cleared now. Considering the quantities of carbon dioxide, carbonmonoxide, methane, nitrous oxide, NO{sub x} and non-methane hydrocarbons released raises the impact by 22--37%. The relative impact on the greenhouse effect of each gas is based on the Intergovernmental Panel on Climate Change (IPCC) calculations over a 20-year time period (including indirect effects). The six gases considered have a combined global warming impact equivalent to 343 to 386 million MT of C0{sub 2}-equivalent carbon, depending on assumptions regarding the release of methane and other gases from the various sources such as burning and termites. These emissions represent 7--8 times the 50 million MT annual carbon release from Brazil`s use of fossil fuels, but bring little benefit to the country. Stopping deforestation in Brazil would prevent as much greenhouse emission as tripling the fuel efficiency of all the automobiles in the world. The relatively cheap measures needed to contain deforestation, together with the many complementary benefits of doing so, make this the first priority for funds intended to slow global warming.

We report the catalytic activity of colloid platinum nanoparticles synthesized with different organic capping layers. On the molecular scale, the porous organic layers have open spaces that permit the reactant and product molecules to reach the metal surface. We carried out CO oxidation on several platinum nanoparticle systems capped with various organic molecules to investigate the role of the capping agent on catalytic activity. Platinum colloid nanoparticles with four types of capping layer have been used: TTAB (Tetradecyltrimethylammonium Bromide), HDA (hexadecylamine), HDT (hexadecylthiol), and PVP (poly(vinylpyrrolidone)). The reactivity of the Pt nanoparticles varied by 30%, with higher activity on TTAB coated nanoparticles and lower activity on HDT, while the activation energy remained between 27-28 kcal/mol. In separate experiments, the organic capping layers were partially removed using ultraviolet light-ozone generation techniques, which resulted in increased catalytic activity due to the removal of some of the organic layers. These results indicate that the nature of chemical bonding between organic capping layers and nanoparticle surfaces plays a role in determining the catalytic activity of platinum colloid nanoparticles for carbonmonoxideoxidation.

Rural Alaska currently uses diesel generator sets to produce much of its power. The high energy content of diesel (i.e. ~140,000 BTU per gallon) makes it the fuel of choice because this reduces the volume of fuel that must be transported, stored, and consumed in generating the power. There is an existing investment in infrastructure for the distribution and use of diesel fuel. Problems do exist, however, in that diesel generators are not very efficient in their use of diesel, maintenance levels can be rather high as systems age, and the environmental issues related to present diesel generators are of concern. The Arctic Energy Technology Development Laboratory at the University of Alaska -- Fairbanks is sponsoring a project to address the issues mentioned above. The project takes two successful systems, a diesel reformer and a tubular solid oxide fuel cell unit, and jointly tests those systems with the objective of producing a for-purpose diesel fueled solid oxide fuel cell system that can be deployed in rural Alaska. The reformer will convert the diesel to a mixture of carbonmonoxide and hydrogen that can be used as a fuel by the fuel cell. The high temperature nature of the solid oxide fuel cell (SOFC is capable of using this mixture to generate electricity and provide usable heat with higher efficiency and lower emissions. The high temperature nature of the SOFC is more compatible with the arctic climate than are low temperature technologies such as the proton exchange membrane fuel cells. This paper will look at the interaction of a SOFC system that is designed to internally reform methane and a catalytic partial oxidation (CPOX) diesel reformer. The diesel reformer produces a reformate that is approximately 140 BTU per scf (after removal of much of the reformate water) as compared to a methane based reformate that is over twice that value in BTU content. The project also considers the effect of altitude since the test location will be at 4800 feet with the consequential drop in oxygen content and necessary increases in flow rates.

when consumed in an internal combustion engine yields no SOX, NOX or carbonmonoxide all environmentally harmful byproducts of combustion. CO2 is the combustion byproduct of butanol, and is considered our nation's dependence on foreign oil, protect our fuel generation grid from sudden disruption while

A microcomputer-based control system utilizing a distributed intelligence architecture has been developed to control combustion in hydrocarbon fuel-fired boilers and heaters to significantly reduce fuel usage. The system incorporates a unique flue...

Sandia National Laboratories, in partnership with the Consumer Product Safety Commission (CPSC), has developed an optical-based sensor for the detection of CO in appliances such as residential furnaces. The device is correlation radiometer based on detection of the difference signal between the transmission spectrum of the sample multiplied by two alternating synthetic spectra (called Eigen spectra). These Eigen spectra are derived from a priori knowledge of the interferents present in the exhaust stream. They may be determined empirically for simple spectra, or using a singular value decomposition algorithm for more complex spectra. Data is presented on the details of the design of the instrument and Eigen spectra along with results from detection of CO in background N{sub 2}, and CO in N{sub 2} with large quantities of interferent CO{sub 2}. Results indicate that using the Eigen spectra technique, CO can be measured at levels well below acceptable limits in the presence of strongly interfering species. In addition, a conceptual design is presented for reducing the complexity and cost of the instrument to a level compatible with consumer products.

efficiency, safety and cost-effectiveness. With this control approach, the existing analog boiler controls remain intact and continue to function. No costly retrofit of computer compatible controllers and actuators is required and full analog backup.... The control output to the boiler control interface, such as a pUlse-to pneumatic converter linked to an air bias station that adjusts the air:fuel ratio, is calculated based on the time domain response of the boiler. The control algorithm recognizes...

of the cluster that reacts with CO. The structure of the active-site C-cluster in CO dehydrogenase from Carboxydothermus hydrogenoformans (CODHCh) includes a ??2-sulfide ion bridged to the Ni and unique Fe, while the same cluster in enzymes from Rhodospirillum...

OAK-B135 Metalloenzymes seem to ''come of age'' when their structures are known at atomic resolution, spectroscopic and catalytic properties are basically understood, and genetic expression systems are available. Such foundations allow detailed mechanistic and spectroscopic properties to be probed and correlated to structure. The objective of this article is to summarize what is known about the title group of enzymes, and show that, to a large degree, they have come of age.

worldwide by outdoor air pollution caused by vehicles and industrial emissions (http://www.who.int; http:// www.infoforhealth.org). Notably, air pollution increases the risk of mortality from cardiovascular investigating the effects of urban air pollution in humans are mainly restricted to epide- miological studies

is discussed. Visual inspection of the crystal structure of CODHRr and CODHCh, along with sequence alignments, indicates that there may be separate pathways for proton and electron transfer during catalysis. Mutants of a proposed proton transfer pathway were...

Previous studies have demonstrated an external source of CO on Jupiter, Saturn, and Neptune. However, it has not been possible to demonstrate this on Uranus because of its low CO abundance, low upper-tropospheric temperatures, and low stratospheric thermal gradient, which make detection very challenging. Here we use 17 Herschel/SPIRE observation sequences spanning 3 yr (2009-2012), which cover 14.6-51.8 cm{sup –1} with a combined integration time of 5 hr. These spectra were originally taken for routine calibration purposes, so were corrected for continuum offsets prior to analysis. The final stacked spectra had an extremely low noise level of 10-50 pW cm{sup –2} sr{sup –1}/cm{sup –1}. Despite this, CO was not observed, but we were able to obtain stringent 3? upper limits at the 0.1-0.2 bar level of 2.1 ppb for a uniform profile, and 9.4 ppb for a stratosphere-only profile—an order of magnitude improvement over previous studies. Comparison with observed CO fluorescence by Encrenaz et al. suggests the majority of Uranus' stratospheric CO has an external origin. It thus appears that external supply of oxygen species—via comets, micrometeorites, or dust—is an important process on all giant planets in our solar system.

, tampering effects and anti-tampering and inspection/maintenance programs. The TEXIN2 model was compared to experimental data near intersections and to corresponding simulations by TEXIN and other existing intersection models. The revised model also... several new capabilities such as T-intersections, one way streets, and four way stops. Other new options include inspection/maintenance capabilities, provision for anti-tampering programs, and a "short-cut" emissions estimate. Finally, the TEXIN...

Succeeding our previous finding about coherent interference of the resonant states of CO^- formed by the low-energy electron attachment [Phys. Rev. A 88, 012708 (2013)], here we provide more evidences of the coherent interference, in particular, we find the state configuration change in the interference with the increase of electron attachment energy by measuring the completely backward distributions of the O^- fragment ion of the temporary CO^- in an energy range 11.3-12.6 eV. Therefore, different pure states, namely, coherent resonances, can be formed when the close-lying resonant states are coherently superposed by a broad-band electron pulse.

A process for synthesis of a catalyst is provided. The process includes providing a carbon precursor material, oxidizing the carbon precursor material whereby an oxygen functional group is introduced into the carbon precursor material, and adding a nitrogen functional group into the oxidizedcarbon precursor material.

The hot pressing of beryllium oxide powder into high density compacts with little or no density gradients is achieved by employing a homogeneous blend of beryllium oxide powder with a lithium oxide sintering agent. The lithium oxide sintering agent is uniformly dispersed throughout the beryllium oxide powder by mixing lithium hydroxide in an aqueous solution with beryllium oxide powder. The lithium hydroxide is converted in situ to lithium carbonate by contacting or flooding the beryllium oxide-lithium hydroxide blend with a stream of carbon dioxide. The lithium carbonate is converted to lithium oxide while remaining fixed to the beryllium oxide particles during the hot pressing step to assure uniform density throughout the compact.

Syngas components hydrogen and carbonmonoxide may be formed by the decomposition of carbon dioxide and water or steam by a solid-oxide electrolysis cell to form carbonmonoxide and hydrogen, a portion of which may be reacted with carbon dioxide to form carbonmonoxide. One or more of the components for the process, such as steam, energy, or electricity, may be provided using a nuclear power source.

A solid oxide fuel cell (SOFC) is a high temperature fuel cell and it normally operates in the range of 850 to 1000 C. Coal syngas has been considered for use in SOFC systems to produce electric power, due to its high temperature and high hydrogen and carbonmonoxide content. However, coal syngas also has contaminants like carbon dioxide (CO{sub 2}) and hydrogen sulfide (H{sub 2}S). Among these contaminants, H{sub 2}S is detrimental to electrode material in SOFC. Commonly used anode material in SOFC system is nickel-yttria stabilized zirconia (Ni-YSZ). The presence of H{sub 2}S in the hydrogen stream will damage the Ni anode and hinder the performance of SOFC. In the present study, an attempt was made to understand the mechanism of anode (Ni-YSZ) deterioration by H{sub 2}S. The study used computation methods such as quantum chemistry calculations and molecular dynamics to predict the model for anode destruction by H{sub 2}S. This was done using binding energies to predict the thermodynamics and Raman spectroscopy to predict molecular vibrations and surface interactions. On the experimental side, a test stand has been built with the ability to analyze button cells at high temperature under syngas conditions.

The present invention relates generally to reinforced carbon nanotubes, and more particularly to reinforced carbon nanotubes having a plurality of microparticulate carbide or oxide materials formed substantially on the surface of such reinforced carbon nanotubes composite materials. In particular, the present invention provides reinforced carbon nanotubes (CNTs) having a plurality of boron carbide nanolumps formed substantially on a surface of the reinforced CNTs that provide a reinforcing effect on CNTs, enabling their use as effective reinforcing fillers for matrix materials to give high-strength composites. The present invention also provides methods for producing such carbide reinforced CNTs.

America and Europe, butwitha lower BC/CO slope. Ambient concentrations indicate high BC emission from South Asia: 2 Panel on Climate Change (IPCC), 1996; National Research Council (NRC), 1996; Jacobson, 2001], but little; published 4 September 2002. [1] Air from South Asia carries heavy loadings of organic and light

The DNA and RNA repair protein AlkB removes alkyl groups from nucleic acids by a unique iron- and ?-ketoglutarate-dependent oxidation strategy. When alkylated adenines are used as AlkB targets, earlier work suggests that ...

This thesis presents a general model for the carbon footprint analysis of advanced wastewater treatment plants (WWTPs) with biological nitrogen removal processes, using a life cycle assessment (LCA) approach. Literature ...

In this work we describe the results of a computer study used to investigate the practicality of several heat exchanger configurations that could be used to extract heat from tubular solid oxide fuel cells (SOFCs) . Two SOFC feed gas compositions were used in this study. They represent product gases from two different coal gasifier designs from the Zero Emission Coal study at Los Alamos National Laboratory . Both plant designs rely on the efficient use of the heat produced by the SOFCs . Both feed streams are relatively rich in hydrogen with a very small hydrocarbon content . One feed stream has a significant carbonmonoxide content with a bit less hydrogen . Since neither stream has a significant hydrocarbon content, the common use of the endothermic reforming reaction to reduce the process heat is not possible for these feed streams . The process, the method, the computer code, and the results are presented as well as a discussion of the pros and cons of each configuration for each process .

The National Energy Technology Laboratory’s Office of Research & Development (NETL/ORD) has successfully demonstrated the operation of a solid oxide fuel cell (SOFC) using reformed biodiesel. The biodiesel for the project was produced and characterized by West Virginia State University (WVSU). This project had two main aspects: 1) demonstrate a catalyst formulation on monolith for biodiesel fuel reforming; and 2) establish SOFC stack test stand capabilities. Both aspects have been completed successfully. For the first aspect, in–house patented catalyst specifications were developed, fabricated and tested. Parametric reforming studies of biofuels provided data on fuel composition, catalyst degradation, syngas composition, and operating parameters required for successful reforming and integration with the SOFC test stand. For the second aspect, a stack test fixture (STF) for standardized testing, developed by Pacific Northwest National Laboratory (PNNL) and Lawrence Berkeley National Laboratory (LBNL) for the Solid Energy Conversion Alliance (SECA) Program, was engineered and constructed at NETL. To facilitate the demonstration of the STF, NETL employed H.C. Starck Ceramics GmbH & Co. (Germany) anode supported solid oxide cells. In addition, anode supported cells, SS441 end plates, and cell frames were transferred from PNNL to NETL. The stack assembly and conditioning procedures, including stack welding and sealing, contact paste application, binder burn-out, seal-setting, hot standby, and other stack assembly and conditioning methods were transferred to NETL. In the future, fuel cell stacks provided by SECA or other developers could be tested at the STF to validate SOFC performance on various fuels. The STF operated on hydrogen for over 1000 hrs before switching over to reformed biodiesel for 100 hrs of operation. Combining these first two aspects led to demonstrating the biodiesel syngas in the STF. A reformer was built and used to convert 0.5 ml/min of biodiesel into mostly hydrogen and carbonmonoxide (syngas.) The syngas was fed to the STF and fuel cell stack. The results presented in this experimental report document one of the first times a SOFC has been operated on syngas from reformed biodiesel.

Nanosized perovskite LaFe?.?Co?.?O? (LFCO) is synthesized through conventional co-precipitation method and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPs-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation has been studied by cyclic voltammetry. Based on the electrochemical studies, all MWCNTs-PtNPs-nafion (or chitosan) and MWCNTs-PtNPs-LFCO-nafion (or chitosan) catalysts show a considerable activity for methanol oxidation. However, a synergistic effect is observed when LFCO is added to the catalyst by decreasing the poisoning rate of the Pt catalyst. - Graphical abstract: Nanosized perovskite LaFe?.?Co?.?O? is synthesized and characterized. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPS-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation is studied. Highlights: • Nanocrystalline LaFe?.?Co?.?O? (LFCO) is prepared by a new simple co-precipitation method. • Effect of LFCO to catalytic activity of PtNPS for methanol oxidation is studied. • A synergistic effect is observed when LFCO is added to the Pt catalyst. • Oxygen of LFCO could be considered as active oxygen to remove CO intermediates.

A method of producing a composite carbon catalyst is generally disclosed. The method includes oxidizing a carbon precursor (e.g., carbon black). Optionally, nitrogen functional groups can be added to the oxidizedcarbon precursor. Then, the oxidizedcarbon precursor is refluxed with a non-platinum transitional metal precursor in a solution. Finally, the solution is pyrolyzed at a temperature of at least about 500.degree. C.

It is well known that the activity, selectivity, and deactivation behavior of heterogeneous catalysts are strongly affected by a wide variety of parameters, including but not limited to nanoparticle size, shape, composition, support, pretreatment conditions, oxidation state, and electronic state. Enormous effort has been expended in an attempt to understand the role of these factors on catalytic behavior, but much still remains to be discovered. In this work, we have focused on deepening the present understanding of the role of nanoparticle shape, nanoparticle composition, and hot electrons on heterogeneous catalysis in the oxidation of carbonmonoxide by molecular oxygen and nitric oxide. These reactions were chosen because they are important for environmental applications, such as in the catalytic converter, and because there is a wide range of experimental and theoretical insight from previous single crystal work as well as experimental data on nanoparticles obtained using new state-of-the-art techniques that aid greatly in the interpretation of results on complex nanoparticle systems. In particular, the studies presented in this work involve three types of samples: {approx} 6.5 nm Rh nanoparticles of different shapes, {approx} 15 nm Rh1-xPdx core-shell bimetallic polyhedra nanoparticles, and Rh ultra-thin film ({approx} 5 nm) catalytic nanodiodes. The colloidal nanoparticle samples were synthesized using a co-reduction of metal salts in alcohol and supported on silicon wafers using the Langmuir-Blodgett technique. This synthetic strategy enables tremendous control of nanoparticle size, shape, and composition. Nanoparticle shape was controlled through the use of different organic polymer capping layers. Bimetallic core-shell nanoparticles were synthesized by careful choice of metal salt precursors. Rh/TiO{sub x} and Rh/GaN catalytic nanodiodes were fabricated using a variety of thin film device fabrication techniques, including reactive DC magnetron sputtering, electron beam evaporation, and rapid thermal annealing. The combination of these techniques enabled control of catalytic nanodiode morphology, geometry, and electrical properties.

Oxidant selection is the highest priority for advanced coal gasification-process development. This paper presents comparative analysis of the Powder River Basin bituminous-coal gasification processes for entrained-flow plasma gasifier. Several oxidants, which might be employed for perspective commercial applications, have been chosen, including air, steam/carbon-dioxide blend, carbon dioxide, steam, steam/air, steam/oxygen, and oxygen. Synthesis gas composition, carbon gasification degree, specific power consumptions, and power efficiency for these processes were determined. The influence of the selected oxidant composition on the gasification-process main characteristics have been investigated.

Photolysis of the hexacarbonyl molecules M(CO)/sub 6/ (M = Cr or W) in the presence of either CO/sub 2/ or N/sub 2/O has been explored by examining the IR, Raman, and UV-visible spectra of solid argon or methane matrices at ca. 20 K. Hence it has been established that the hexacarbonyl undergoes photooxidation at the hands of CO/sub 2/ or N/sub 2/O, the reaction proceeding in three stages. First, photolysis gives rise to a complex of the type XO-M(CO)/sub 5/ (X = OC or N/sub 2/), which is photochromic, being readily converted to Y-M(CO)/sub 5/ (Y = Ar, CH/sub 4/) and M(CO)/sup 6/ with the release of CO/sub 2/ or N/sub 2/O. Second, complexing activates the CO/sub 2/ or N/sub 2/O molecule to photodissociation at wavelengths far in excess of the normal thresholds, so that continued UV photolysis leads to oxidation of the metal carbonyl to oxo-metal carbonyl intermediates O/sub x/M(CO)/sub y/ containing M=O groups, e.g. trans-O/sub 2/W(CO)/sub 4/; there is simultaneous reduction of CO/sub 2/ to CO and of N/sub 2/O to N/sub 2/. In addition, Cr(CO)/sub 6/ but not W(CO)/sub 6/ gives what is believed to be a binuclear intermediate incorporating CO/sub 2/. Finally, after prolonged UV photolysis, oxidation of the metal carbonyls affords the binary metal oxide molecules CrO/sub 2/ and WO/sub 3/. 44 references, 6 figures, 3 tables.

The primary objective of this project had been the investigation of the effects of pore structure on the capacity of porous metal oxides for removal of gaseous pollutants from flue gases of power plants (SO{sub 2}) and hot coal gas (primarily H{sub 2}S). Porous calcines obtained from natural precursors (limestones and dolomites) and sorbents based on zinc oxide were used as model systems in our experimental studies, which included reactivity evolution experiments and pore structure characterization using a variety of methods. The key idea behind this project was to appropriately exploit the differences of the sulfidation and sulfation reactions (for instance, different molar volumes of solid products) to elucidate the dependence of the sorptive capacity of a porous sorbent on its physical microstructure. In order to be able to proceed faster and more productively on the analysis of the above defined problem, it was decided to employ in our studies solids whose reaction with SO{sub 2} (limestone calcines) or H{sub 2}S (sorbents based on zinc oxide) had been investigated in detail in past studies by our research group. Reactivity vs time or conversion vs time studies were conducted using thermogravimetry and fixed-bed and fluidized-bed reactors. The pore structure of partially reacted samples collected at selected time instants or conversion levels was analyzed by gas adsorption and mercury porosimetry. For better characterization of the pore structure of the solid samples, we also carried out intraparticle diffusivity measurements by the peak-broadening (chromatographic) method, using a system developed for this purpose in our laboratory. In the context of this part of the project, we also conducted a detailed theoretical investigation of the measurement of effective diffusivities in porous solids using the diffusion-cell method.

An ablation resistant, monolithic, activated, carbon foam produced by the activation of a coal-based carbon foam through the action of carbon dioxide, ozone or some similar oxidative agent that pits and/or partially oxidizes the carbon foam skeleton, thereby significantly increasing its overall surface area and concurrently increasing its filtering ability. Such activated carbon foams are suitable for application in virtually all areas where particulate or gel form activated carbon materials have been used. Such an activated carbon foam can be fabricated, i.e. sawed, machined and otherwise shaped to fit virtually any required filtering location by simple insertion and without the need for handling the "dirty" and friable particulate activated carbon foam materials of the prior art.

A thermal method to passivate the carbon and/or other components in fly ash significantly decreases adsorption. The passivated carbon remains in the fly ash. Heating the fly ash to about 500 and 800 degrees C. under inert gas conditions sharply decreases the amount of surfactant adsorbed by the fly ash recovered after thermal treatment despite the fact that the carbon content remains in the fly ash. Using oxygen and inert gas mixtures, the present invention shows that a thermal treatment to about 500 degrees C. also sharply decreases the surfactant adsorption of the recovered fly ash even though most of the carbon remains intact. Also, thermal treatment to about 800 degrees C. under these same oxidative conditions shows a sharp decrease in surfactant adsorption of the recovered fly ash due to the fact that the carbon has been removed. This experiment simulates the various "carbon burnout" methods and is not a claim in this method. The present invention provides a thermal method of deactivating high carbon fly ash toward adsorption of AEAs while retaining the fly ash carbon. The fly ash can be used, for example, as a partial Portland cement replacement in air-entrained concrete, in conductive and other concretes, and for other applications.

Polyacrylonitrile (PAN)-based carbon paper with fiber diameters of 200–300 nm was developed through hot-pressing, pre-oxidation, and carbonization of electrospun fiber mats. Changes in morphology, crystallinity, and surface ...

Ultraviolet absorption cross sections of the main and substituted sulfur monoxide (SO) isotopologues were calculated using R-Matrix expansion technique. Energies, transition dipole moments, and nonadiabatic coupling matrix elements were calculated at MRCI/AV6Z level. The calculated absorption cross section of {sup 32}S{sup 16}O was compared with experimental spectrum; the spectral feature and the absolute value of photoabsorption cross sections are in good agreement. Our calculation predicts a long lived photoexcited SO* species which causes large non-mass dependent isotopic effects depending on the excitation energy in the ultraviolet region.

Even before the Clean Air Act Amendments of 1990, regulatory authorities monitored and regulated a number of pollutants: lead, carbonmonoxide, oxides of sulfur, oxides of nitrogen, ozone and PM-10. The Clean Air Act Amendments increased the focus...

The main goal of this project had been to use model systems to correlate selectivities in partial oxidation catalysis with the presence of specific sites on the surface of the catalyst. Extensive work was performed this year on characterizing oxygen-treated nickel surfaces by chemical means. Specifically, the surface chemistry of ammonia coadsorbed with atomic oxygen on Ni(110) single-crystal surfaces was studied by temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). It was determined that at intermediate oxygen coverages direct ammonia adsorption on nickel sites is suppressed, but a new high-temperature reaction regime is generated at 400 K where NHx surface fragments are rehydrogenated concurrently with the production of water and molecular hydrogen. The extensive isotope scrambling and hydrogen transfer seen from nitrogen- to oxygen-containing surface intermediates, and the optimum yields seen for this 400 K state at intermediate oxygen coverages, strongly suggest the direct interaction of the adsorbed ammonia with oxygen atoms at the end of the –Ni–O- rows that form upon reconstruction of the surface. Hydrogen transfer between ammonia and oxygen appears to take place directly via hydrogen bonding, and to be reversible but biased towards water formation. An equilibrium is reached between the produced water and the reacting surface oxygen and hydrogen. The strong influence of the OH surface groups on the thermal chemistry of the adsorbed ammonia was interpreted in terms of the adsorbing geometry of the OH groups on the surface, and of hydrogen bonding between adsorbed OH and NH3 species. In terms of alcohol reactivity, the adsorption of 2-iodoethanol, a precursor for the preparation of 2-hydroxyethyl and oxametallacycle surface species, was found to lead to two configurations involving either just the iodine atom or both iodine and hydroxyl ends of the molecule. A complex chemical behavior starts around 140 K with the production of small amounts of ethylene and water, most likely via the concerted decomposition or disproportionation of the adsorbed molecular species. The bulk of the 2-iodoethanol decomposes at about 150 K via an initial carbon-iodine scission to form –O(H)CH2CH2– (~80%) and 2-hydroxyethyl (~20%) intermediates. Two competing reactions are involved with the subsequent conversion of the 2-hydroxyethyl species around 160 K, a reductive elimination with surface hydrogen to yield ethanol, and a ?-H elimination to surface vinyl alcohol. The –O(H)CH2CH2–, on the other hand, dehydrogenates to a –OCH2CH2– oxametallacycle species about the same temperature. Both 2-hydroxyethyl and oxametallacycle species tautomerize to acetaldehyde, around 210 K and above 250 K, respectively, and some of that acetaldehyde desorbs while the rest decomposes to hydrogen and carbonmonoxide. We contend that a better understanding of the surface chemistry of oxygen-containing surfaces can lead to better selectivities in catalysis. This is arguably the most important issue in the field of catalysis in the near future, and one that impacts several technologies of interest to DOE such as the manufacturing of speciality chemicals and the control and removal of pollutants. Additional work was performed on the characterization of the chemistry of methyl and methylene adsorbed species on oxygen-treated nickel surfaces. Complex chemistry was observed involving not only hydrogenation and dehydrogenation steps, but also C-C couplings and methylene insertions to produce heavier hydrocarbons, and oxygen insertion reactions that yield oxygenates. Finally, a dual titration technique employing xenon and a chemically sensitive probe was developed to identify minority catalytic sites on oxide surfaces. In the case of oxygen-treated Ni(110) single crystals, it was found that both hydrogen transfer with adsorbed water or ammonia and certain hydrocarbon hydrogenation reactions take place at the end of the –Ni–O rows that form in this system. Carbon and nitrogen oxides, on the other hand, display no pre

This report summarizes the results of both experimental and modeling studies performed using Sludge Batch 10 (SB10) simulants and FBSR product from Tank 48 simulant testing in order to develop higher levels of coal-carbon that can be managed by DWPF. Once the Fluidized Bed Steam Reforming (FBSR) process starts up for treatment of Tank 48 legacy waste, the FBSR product stream will contribute higher levels of coal-carbon in the sludge batch for processing at DWPF. Coal-carbon is added into the FBSR process as a reductant and some of it will be present in the FBSR product as unreacted coal. The FBSR product will be slurried in water, transferred to Tank Farm and will be combined with sludge and washed to produce the sludge batch that DWPF will process. The FBSR product is high in both water soluble sodium carbonate and unreacted coal-carbon. Most of the sodium carbonate is removed during washing but all of the coal-carbon will remain and become part of the DWPF sludge batch. A paper study was performed earlier to assess the impact of FBSR coal-carbon on the DWPF Chemical Processing Cell (CPC) operation and melter off-gas flammability by combining it with SB10-SB13. The results of the paper study are documented in Ref. 7 and the key findings included that SB10 would be the most difficult batch to process with the FBSR coal present and up to 5,000 mg/kg of coal-carbon could be fed to the melter without exceeding the off-gas flammability safety basis limits. In the present study, a bench-scale demonstration of the DWPF CPC processing was performed using SB10 simulants spiked with varying amounts of coal, and the resulting seven CPC products were fed to the DWPF melter cold cap and off-gas dynamics models to determine the maximum coal that can be processed through the melter without exceeding the off-gas flammability safety basis limits. Based on the results of these experimental and modeling studies, the presence of coal-carbon in the sludge feed to DWPF is found to have both positive (+) and negative (-) impact as summarized below: (-) Coal-carbon is a melter reductant. If excess coal-carbon is present, the resulting melter feed may be too reducing, potentially shortening the melter life. During this study, the Reduction/Oxidation Potential (REDOX) of the melter could be controlled by varying the ratio of nitric and formic acid. (-) The addition of coal-carbon increases the amount of nitric acid added and decreases the amount of formic acid added to control melter REDOX. This means that the CPC with the FBSR product is much more oxidizing than current CPC processing. In this study, adequate formic acid was present in all experiments to reduce mercury and manganese, two of the main goals of CPC processing. (-) Coal-carbon will be oxidized to carbon dioxide or carbonmonoxide in the melter. The addition of coal-carbon to the FBSR product will lead to approximately 55% higher offgas production from formate, nitrate and carbon due to the decomposition of the carbon at the maximum levels in this testing. Higher offgas production could lead to higher cold cap coverage or melter foaming which could decrease melt rate. No testing was performed to evaluate the impact of the higher melter offgas flow. (+) The hydrogen production is greatly reduced in testing with coal as less formic acid is added in CPC processing. In the high acid run without coal, the peak hydrogen generation was 15 times higher than in the high acid run with added coal-carbon. (+) Coal-carbon is a less problematic reducing agent than formic acid, since the content of both carbon and hydrogen are important in evaluating the flammability of the melter offgas. Processing with coal-carbon decreases the amount of formic acid added in the CPC, leading to a lower flammability risk in processing with coal-carbon compared to the current DWPF flowsheet. (+) The seven SB10 formulations which were tested during the bench-scale CPC demonstration were all determined to be within the off-gas flammability safety basis limits during the 9X/5X off-gas surge for normal bubbled melter

We report and solidly interpret the infrared spectrum of both pristine and oxidized carbynes embedded in a pure-carbon matrix. The spectra probe separately the effects of oxidation on sp- and on sp{sup 2}-hybridized carbon, and provide information on the stability of the different structures in an oxidizing atmosphere. The final products are mostly short end-oxidized carbynes anchored with a double bond to sp{sup 2} fragments, plus an oxidized sp{sup 2} amorphous matrix. Our results have important implications for the realization of carbyne-based nano-electronics devices and highlight the active participation of carbynes in astrochemical reactions where they act as carbon source for the promotion of more complex organic species.

A new catalyst offers a new way to enhance mercury control from bituminous coal-fired power plants. Hitachi has developed an SCR catalyst which satisfies high Hg{sup 0} oxidation and low SO{sub 2} oxidation requirements under high temperatures (716 to 770 F). This triple action catalysts, TRAC can significantly enhance mercury oxidation and reduce or eliminate the need for additional mercury control measures such as activated carbon injection. After laboratory testing, pilot-scale tests confirmed an activity of 1.4-1.7 times higher than that of conventional SCR catalyst. The new catalyst has been successfully applied in a commercial PRB-fired boiler without the need for halogens to be added to the fuel feed or flue gas. 2 figs.

A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

The oxidation of methyl formate (CH{sub 3}OCHO) has been studied in three experimental environments over a range of applied combustion relevant conditions: 1. A variable-pressure flow reactor has been used to quantify reactant, major intermediate and product species as a function of residence time at 3 atm and 0.5% fuel concentration for oxygen/fuel stoichiometries of 0.5, 1.0, and 1.5 at 900 K, and for pyrolysis at 975 K. 2. Shock tube ignition delays have been determined for CH{sub 3}OCHO/O{sub 2}/Ar mixtures at pressures of ? 2.7, 5.4, and 9.2 atm and temperatures of 1275–1935 K for mixture compositions of 0.5% fuel (at equivalence ratios of 1.0, 2.0, and 0.5) and 2.5% fuel (at an equivalence ratio of 1.0). 3. Laminar burning velocities of outwardly propagating spherical CH{sub 3}OCHO/air flames have been determined for stoichiometries ranging from 0.8–1.6, at atmospheric pressure using a pressure-release-type high-pressure chamber. A detailed chemical kinetic model has been constructed, validated against, and used to interpret these experimental data. The kinetic model shows that methyl formate oxidation proceeds through concerted elimination reactions, principally forming methanol and carbonmonoxide as well as through bimolecular hydrogen abstraction reactions. The relative importance of elimination versus abstraction was found to depend on the particular environment. In general, methyl formate is consumed exclusively through molecular decomposition in shock tube environments, while at flow reactor and freely propagating premixed flame conditions, there is significant competition between hydrogen abstraction and concerted elimination channels. It is suspected that in diffusion flame configurations the elimination channels contribute more significantly than in premixed environments.

A process for the production of a pollutant-free particulate carbon (i.e., a substantially ash-, sulfur- and nitrogen-free carbon) from carbonaceous feedstocks. The basic process involves de-oxygenating one of the gas streams formed in a cyclic hydropyrolysis-methane pyrolysis process in order to improve conversion of the initial carbonaceous feedstock. De-oxygenation is effected by catalytically converting carbonmonoxide, carbon dioxide, and hydrogen contained in one of the pyrolysis gas streams, preferably the latter, to a methanol co-product. There are thus produced two products whose use is known per se, viz., a substantially pollutant-free particulate carbon black and methanol. These products may be admixed in the form of a liquid slurry of carbon black in methanol.

A process is described for the production of a pollutant-free particulate carbon (i.e., a substantially ash-, sulfur- and nitrogen-free carbon) from carbonaceous feedstocks. The basic process involves de-oxygenating one of the gas streams formed in a cyclic hydropyrolysis-methane pyrolysis process in order to improve conversion of the initial carbonaceous feedstock. De-oxygenation is effected by catalytically converting carbonmonoxide, carbon dioxide, and hydrogen contained in one of the pyrolysis gas streams, preferably the latter, to a methanol co-product. There are thus produced two products whose use is known per se, viz., a substantially pollutant-free particulate carbon black and methanol. These products may be admixed in the form of a liquid slurry of carbon black in methanol. 3 figs.

In this July 9, 2010 Berkeley Lab summer lecture, Lab scientists Jeff Long of the Materials Sciences and Nancy Brown of the Environmental Energy Technologies Division discuss their efforts to fight climate change by capturing carbon from the flue gas of power plants, as well as directly from the air

Bimetallic Cluster Provides a Higher Activity Electrocatalyst for Methanol Oxidation* Brenda L:Ru nanoparticles on carbon (PtRu/C) for use as an electrocatalyst for methanol oxidation. This bimetallic carbonyl support particles. Cyclic voltammo- grams of methanol oxidation from the two catalysts showed

We report the detection of shock-excited far-infrared emission of H2O, OH, and CO from the supernova remnant 3C 391, using the ISO Long-Wavelength Spectrometer. This is the first detection of thermal H2O and OH emission from a supernova remnant. For two other remnants, W~28 and W~44, CO emission was detected but OH was only detected in absorption. The observed H2O and OH emission lines arise from levels within ~400 K of the ground state, consistent with collisional excitation in warm, dense gas created after the passage of the shock front through the dense clumps in the pre-shock cloud. The post-shock gas we observe has a density ~2x10^5 cm^{-3} and temperature 100-1000 K, and the relative abundances of CO:OH:H2O in the emitting region are 100:1:7 for a temperature of 200 K. The presence of a significant column of warm H2O suggests that the chemistry has been significantly changed by the shock. The existence of significant column densities of both OH and H2O, which is at odds with models for non-dissociative shocks into dense gas, could be due to photodissociation of H2O or a mix of fast and slow shocks through regions with different pre-shock density.

CDIAC products are indexed and searchable through a customized interface powered by ORNL's Mercury search engine. Products include numeric data packages, publications, trend data, atlases, models, etc. and can be searched for by subject area, keywords, authors, product numbers, time periods, collection sites, spatial references, etc. Some of the collections may also be included in the CDIAC publication, Trends Online: A Compendium of Global Change Data. Most data sets, many with numerous data files, are free to download from CDIAC's ftp area. The collections under the CDIAC heading of Atmospheric Trace Gases include: Atmospheric Carbon Dioxide, Atmospheric Methane, Atmospheric CarbonMonoxide, Atmospheric Hydrogen, Isotopes in Greenhouse Gases, Radionuclides, Aerosols, and Other Trace Gases.

A method for making near-net-shape, monolithic carbon electrodes for energy storage devices. The method includes the controlled pyrolysis and activation of a pressed shape of methyl cellulose powder with pyrolysis being carried out in two stages; pre-oxidation, preferably in air at a temperature between 200.degree.-250.degree. C., followed by carbonization under an inert atmosphere. An activation step to adjust the surface area of the carbon shape to a value desirable for the application being considered, including heating the carbon shape in an oxidizing atmosphere to a temperature of at least 300.degree. C., follows carbonization.

A method is described for making near-net-shape, monolithic carbon electrodes for energy storage devices. The method includes the controlled pyrolysis and activation of a pressed shape of methyl cellulose powder with pyrolysis being carried out in two stages; pre-oxidation, preferably in air at a temperature between 200--250 C, followed by carbonization under an inert atmosphere. An activation step to adjust the surface area of the carbon shape to a value desirable for the application being considered, including heating the carbon shape in an oxidizing atmosphere to a temperature of at least 300 C, follows carbonization. 1 fig.

Molten oxide electrolysis (MOE) is a carbon-neutral, electrochemical technique to decompose metal oxide directly into liquid metal and oxygen gas upon use of an inert anode. What sets MOE apart from other technologies is ...

Molten oxide electrolysis (MOE) is a carbon-free, electrochemical technique to decompose a metal oxide directly into liquid metal and oxygen gas. From an environmental perspective what makes MOE attractive is its ability ...

The electric dipole moment of the electron (eEDM) is a signature of CP-violating physics beyond the Standard Model. We describe an ongoing experiment to measure or set improved limits to the eEDM, using a cold beam of thorium monoxide (ThO) molecules. The metastable $H {}^3\\Delta_1$ state in ThO has important advantages for such an experiment. We argue that the statistical uncertainty of an eEDM measurement could be improved by as much as 3 orders of magnitude compared to the current experimental limit, in a first-generation apparatus using a cold ThO beam. We describe our measurements of the $H$ state lifetime and the production of ThO molecules in a beam, which provide crucial data for the eEDM sensitivity estimate. ThO also has ideal properties for the rejection of a number of known systematic errors; these properties and their implications are described.

Black Carbon Emissions by Rocket Engines Types of rocket engines Emissions Liquid Hydrogen) and tetroxide (24) Large amounts of nitrogen oxides. Kerosene Rockets 2 and black carbon (soot). Focus: New carbon in the stratosphere. The large amount of black carbon emitted by these engines is caused

A method for treating an organic polymer material, preferably a vinylidene chloride/vinyl chloride copolymer (Saran) to produce a flat sheet of carbon film material having a high surface area ([approx equal]1000 m[sup 2] /g) suitable as an electrode material for super capacitor applications. The method comprises heating a vinylidene chloride/vinyl chloride copolymer film disposed between two spaced apart graphite or ceramic plates to a first temperature of about 160 C for about 14 hours to form a stabilized vinylidene chloride/vinyl chloride polymer film, thereafter heating the stabilized film to a second temperature of about 750 C in an inert atmosphere for about one hour to form a carbon film; and finally activating the carbon film to increase the surface area by heating the carbon film in an oxidizing atmosphere to a temperature of at least 750--850 C for between 1--6 hours. 2 figs.

Heme oxygenase (HO) is an enzyme that facilitates the oxidative breakdown of free heme into equi-molar concentrations of carbonmonoxide (CO), the bile pigment biliverdin IX and free iron. These products have immuno-modulatory ...

A method of preparing a porous cathode structure for use in a molten carbonate fuel cell begins by providing a porous integral plaque of sintered nickel oxide particles. The nickel oxide plaque can be obtained by oxidizing a sintered plaque of nickel metal or by compacting and sintering finely divided nickel oxide particles to the desired pore structure. The porous sintered nickel oxide plaque is contacted with a lithium salt for a sufficient time to lithiate the nickel oxide structure and thus enhance its electronic conductivity. The lithiation can be carried out either within an operating fuel cell or prior to assembling the plaque as a cathode within the fuel cell.

A hollow partition wall is employed to feed carbon material to an underflow of a carbothermic reduction furnace used to make aluminum. The partition wall divides a low temperature reaction zone where aluminum oxide is reacted with carbon to form aluminum carbide and a high temperature reaction zone where the aluminum carbide and remaining aluminum oxide are reacted to form aluminum and carbonmonoxide.

Air oxidation studies of Fe-18Cr-18Mn stainless steels were conducted at 525°C, 625°C, and 725°C. Alloys were evaluated with respect to changes in oxidation properties as a result of interstitial additions of nitrogen and carbon and of minor solute additions of silicon, molybdenum, and nickel. Interstitial concentrations possibly had a small, positive effect on oxidation resistance. Minor solute additions significantly improved oxidation resistance but could also reduce interstitial solubility resulting in formation of chromium carbides. Loss of solute chromium resulted in a slight reduction in oxidation protection. Oxidation lasting over 500 hours produced a manganese rich, duplex oxide structure: an outer sesquioxide and an inner spinel oxide.

A carbon corrosion model is developed based on the formation of surface oxides on carbon and platinum of the polymer electrolyte membrane fuel cell electrode. The model predicts the rate of carbon corrosion under potential hold and potential cycling conditions. The model includes the interaction of carbon surface oxides with transient species like OH radicals to explain observed carbon corrosion trends under normal PEM fuel cell operating conditions. The model prediction agrees qualitatively with the experimental data supporting the hypothesis that the interplay of surface oxide formation on carbon and platinum is the primary driver of carbon corrosion.

The oxidation of 2-deoxyribose in DNA has emerged as a critical determinant of the cellular toxicity of oxidative damage to DNA, with oxidation of each carbon producing a unique spectrum of electrophilic products. We have ...

Oblique angle deposited (OAD) silicon monoxide (SiO) thin films forming tilted columnar structures have been characterized by second-harmonic generation. It was found that OAD SiO leads to a rotationally anisotropic second-harmonic response, depending on the optical angle of incidence. A model for the observed dependence of the second-harmonic signal on optical angle of incidence allows extraction of the growth direction of OAD films. The optically determined growth directions show convincing agreement with cross-sectional scanning electron microscopy images. In addition to a powerful characterization tool, these results demonstrate the possibilities for designing nonlinear optical devices through SiO OAD.

oxidized to nitrates. The direct study of the changes in organic matter or carbon in the soil is more satisfactory than any assumption. A considerable amount of work upon the oxidation of organic matter in the soil has been clone hy Wollny... cflpo8city, so the re1ati~-e power of the soil to support oxidizing organisms ma!r he termed its oxidafion cnpaciiy. The nitrif-ing capac- it" the oxidatioa capacity 'and the capacit~ of the soil to convert am- monia into nitrates and ammonia are to a...

This quarterly report discusses the technical progress of a US Department of Energy (DOE) Innovative Clean Coal Technology (ICCT) Project demonstrating advanced tangentially-fired combustion techniques for the reduction of nitrogen oxide (NO{sub x}) emissions from a coal-fired boiler. The project is being conducted at Gulf Power Company`s Plant Lansing Smith Unit 2 located near Panama City, Florida. The primary objective of this demonstration is to determine the long-term effects of commercially available tangentially-fired low NO{sub x} combustion technologies on NO{sub x} emissions and boiler performance. A target of achieving fifty percent NO{sub x} reduction using combustion modifications has been established for the project. The stepwise approach that is being used to evaluate the NO{sub x} control technologies requires three plant outages to successively install the test instrumentation and the different levels of the low NO{sub x} concentric firing system (LNCFS). Following each outage, a series of four groups of tests are performed. These are (1) diagnostic, (2) performance, (3) long-term, and (4) verification. These tests are used to quantify the NO{sub x} reductions of each technology and evaluate the effects of those reductions on other combustion parameters such as particulate characteristics and boiler efficiency. This technical progess report presents the LNCFS Level III long-term data collected during this quarter. NO{sub x} emissions for each day of long-term testing are presented. The average NO{sub x} emission during long-term testing was 0.39 lb/MBtu at an average load of 155 MW. The effect of the low NO{sub x} combustion system on other combustion parameters such as carbonmonoxide, excess oxygen level, and carbon carryover are also included.

This quarterly report discusses the technical progress of a US Department of Energy (DOE) Innovative Clean Coal Technology (ICCT) Project demonstrating advanced tangentially-fired combustion techniques for the reduction of nitrogen oxide (NO[sub x]) emissions from a coal-fired boiler. The project is being conducted at Gulf Power Company's Plant Lansing Smith Unit 2 located near Panama City, Florida. The primary objective of this demonstration is to determine the long-term effects of commercially available tangentially-fired low NO[sub x] combustion technologies on NO[sub x] emissions and boiler performance. A target of achieving fifty percent NO[sub x] reduction using combustion modifications has been established for the project. The stepwise approach that is being used to evaluate the NO[sub x] control technologies requires three plant outages to successively install the test instrumentation and the different levels of the low NO[sub x] concentric firing system (LNCFS). Following each outage, a series of four groups of tests are performed. These are (1) diagnostic, (2) performance, (3) long-term, and (4) verification. These tests are used to quantify the NO[sub x] reductions of each technology and evaluate the effects of those reductions on other combustion parameters such as particulate characteristics and boiler efficiency. This technical progess report presents the LNCFS Level III long-term data collected during this quarter. NO[sub x] emissions for each day of long-term testing are presented. The average NO[sub x] emission during long-term testing was 0.39 lb/MBtu at an average load of 155 MW. The effect of the low NO[sub x] combustion system on other combustion parameters such as carbonmonoxide, excess oxygen level, and carbon carryover are also included.

Separate abstracts were prepared for the 15 papers presented in this workshop report. The state of knowledge about the role of rivers in the transport, storage and oxidation of carbon is the subject of this report. (KRM)

Solid-oxide electrochemical cells are an exciting new technology. Development of solid-oxide cells (SOCs) has advanced considerable in recent years and continues to progress rapidly. This thesis studies several aspects of SOCs and contributes useful information to their continued development. This LDRD involved a collaboration between Sandia and the Colorado School of Mines (CSM) ins solid-oxide electrochemical reactors targeted at solid oxide electrolyzer cells (SOEC), which are the reverse of solid-oxide fuel cells (SOFC). SOECs complement Sandia's efforts in thermochemical production of alternative fuels. An SOEC technology would co-electrolyze carbon dioxide (CO{sub 2}) with steam at temperatures around 800 C to form synthesis gas (H{sub 2} and CO), which forms the building blocks for a petrochemical substitutes that can be used to power vehicles or in distributed energy platforms. The effort described here concentrates on research concerning catalytic chemistry, charge-transfer chemistry, and optimal cell-architecture. technical scope included computational modeling, materials development, and experimental evaluation. The project engaged the Colorado Fuel Cell Center at CSM through the support of a graduate student (Connor Moyer) at CSM and his advisors (Profs. Robert Kee and Neal Sullivan) in collaboration with Sandia.

We report that iron-reducing bacteria are primary mediators of anaerobic carbonoxidation in upland tropical soils spanning a rainfall gradient (3500 - 5000 mm yr-1) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally dynamic redox conditions make iron-transforming microbial communities central to the belowground carbon cycle in these wet tropical forests. The exceedingly high abundance of iron-reducing bacteria (up to 1.2 x 10{sup 9} cells per gram soil) indicated that they possess extensive metabolic capacity to catalyze the reduction of iron minerals. In soils from the higher rainfall sites, measured rates of ferric iron reduction could account for up to 44 % of organic carbonoxidation. Iron reducers appeared to compete with methanogens when labile carbon availability was limited. We found large numbers of bacteria that oxidize reduced iron at sites with high rates of iron reduction and large numbers of iron-reducers. the coexistence of large populations of ironreducing and iron-oxidizing bacteria is evidence for rapid iron cycling between its reduced and oxidized states, and suggests that mutualistic interactions among these bacteria ultimately fuel organic carbonoxidation and inhibit CH4 production in these upland tropical forests.

The presence of carbon in fly ash requires an increase in the dosage of the air-entraining admixture for concrete mix, and may cause the admixture to lose efficiency. Specifying authorities for the concrete producers have set maximum allowable levels of residual carbon. These levels are the so called Loss On Ignition (LOI). The concrete producers` day-to-day purchasing decisions sets the LOI at 4%. The objective of the project is to investigate the kinetics of oxidation of residual carbon present in coal fly ash as a possible first step toward producing low-carbon fly ash from high-carbon, low quality fly ash.

Methods for producing reinforced carbon nanotubes having a plurality of microparticulate carbide or oxide materials formed substantially on the surface of such reinforced carbon nanotubes composite materials are disclosed. In particular, the present invention provides reinforced carbon nanotubes (CNTs) having a plurality of boron carbide nanolumps formed substantially on a surface of the reinforced CNTs that provide a reinforcing effect on CNTs, enabling their use as effective reinforcing fillers for matrix materials to give high-strength composites. The present invention also provides methods for producing such carbide reinforced CNTs.

Carbon supercapacitors are represented as distributed RC networks with transmission line equivalent circuits. At low charge/discharge rates and low frequencies these networks approximate a simple series R{sub ESR}C circuit. The energy efficiency of the supercapacitor is limited by the voltage drop across the ESR. The pore structure of the carbon electrode defines the electrochemically active surface area which in turn establishes the volume specific capacitance of the carbon material. To date, the highest volume specific capacitance reported for a supercapacitor electrode is 220F/cm{sup 3} in aqueous H{sub 2}SO{sub 4} (10) and {approximately}60 F/cm{sup 3} in nonaqueous electrolyte (8).

A carbon microtube comprising a hollow, substantially tubular structure having a porous wall, wherein the microtube has a diameter of from about 10 .mu.m to about 150 .mu.m, and a density of less than 20 mg/cm.sup.3. Also described is a carbon microtube, having a diameter of at least 10 .mu.m and comprising a hollow, substantially tubular structure having a porous wall, wherein the porous wall comprises a plurality of voids, said voids substantially parallel to the length of the microtube, and defined by an inner surface, an outer surface, and a shared surface separating two adjacent voids.

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbonmonoxide and hydrogen or from carbonmonoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbonmonoxide containing gas to a product which could substitute for high density polyethylene.

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbonmonoxide and hydrogen or from carbonmonoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbonmonoxide containing gas to a product which could substitute for high density polyethylene.

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbonmonoxide and hydrogen or from carbonmonoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbonmonoxide containing gas to a product which could substitute for high density polyethylene.

Western Research Institute is developing concepts to use radio frequency (RF) energy to remove NO and SO{sub 2} from combustion flue gas. Char produced from the mild gasification of coal can be heated with RF energy to react with sulfur oxides and nitric oxide at low temperatures and pressures using RF energy to form carbon dioxide, carbonmonoxide, elemental sulfur, and nitrogen.

Western Research Institute is developing concepts to use radio frequency (RF) energy to remove NO and SO{sub 2} from combustion flue gas. Char produced from the mild gasification of coal can be heated with RF energy to react with sulfur oxides and nitric oxide at low temperatures and pressures using RF energy to form carbon dioxide, carbonmonoxide, elemental sulfur, and nitrogen.

A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of {beta}-diketones, halogenated {beta}-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process. 4 figs.

A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones, halogenated .beta.-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process.

adsorbed oxygens which mostly lead to the formation of carbonoxides [1]. In usual fixed or fluidised bed. The oxidation of n- butane to maleic anhydride in a circulating fluid bed reactor was the first industrial

Steam gasification of carbon residue in bed solids of a low-temperature black liquor gasifier was studied using a thermogravimetric system at 3 bar. Complete gasification of the carbon residue, which remained unreactive at 600 C, was achieved in about 10 min as the temperature increased to 800 C. The rate of gasification and its temperature dependence were evaluated from the non-isothermal experiment results. Effects of particle size and adding H{sub 2} and CO to the gasification agent were also studied. The rate of steam gasification could be taken as zero order in carbon until 80% of carbon was gasified, and for the rest of the gasification process the rate appeared to be first order in carbon. The maximum rate of carbon conversion was around 0.003/s and the activation energy was estimated to be in the range of 230-300 kJ/mol. The particle size did not show significant effect on the rate of gasification. Hydrogen and carbonmonoxide appeared to retard the onset of the gasification process. (author)

A method for producing liquid fuels includes the steps of gasifying a starting material selected from a group consisting of coal, biomass, carbon nanotubes and mixtures thereof to produce a syngas, subjecting that syngas to Fischer-Tropsch synthesis (FTS) to produce a hyrdrocarbon product stream, separating that hydrocarbon product stream into C1-C4 hydrocarbons and C5+ hydrocarbons to be used as liquid fuels and subjecting the C1-C4 hydrocarbons to catalytic dehydrogenation (CDH) to produce hydrogen and carbon nanotubes. The hydrogen produced by CDH is recycled to be mixed with the syngas incident to the FTS reactor in order to raise the hydrogen to carbonmonoxide ratio of the syngas to values of 2 or higher, which is required to produce liquid hydrocarbon fuels. This is accomplished with little or no production of carbon dioxide, a greenhouse gas. The carbon is captured in the form of a potentially valuable by-product, multi-walled carbon nanotubes (MWNT), while huge emissions of carbon dioxide are avoided and very large quantities of water employed for the water-gas shift in traditional FTS systems are saved.

Most paved roads in the United States are surfaced with asphalt. These asphalt pavements suffer from fatigue cracking and thermal cracking, aggravated by the oxidation and hardening of asphalt. This negative impact of asphalt oxidation on pavement...

Carbon Trading, Carbon Taxes and Social Discounting Elisa Belfiori belf0018@umn.edu University of Minnesota Abstract This paper considers the optimal design of policies to carbon emissions in an economy, such as price or quantity controls on the net emissions of carbon, are insufficient to achieve the social

The present invention is a method and apparatus for altering a carbon containing compound in an aqueous mixture. According to a first aspect of the present invention, it has been discovered that for an aqueous mixture having a carbon containing compound with an ozone reaction rate less than the ozone reaction rate of pentachlorophenol, use of corona discharge in a low or non-oxidizing atmosphere increases the rate of destruction of the carbon containing compound compared to corona discharge an oxidizing atmosphere. For an aqueous mixture containing pentachlorphenol, there was essentially no difference in destruction between atmospheres. According to a second aspect of the present invention, it has been further discovered that an aqueous mixture having a carbon containing compound in the presence of a catalyst and oxygen resulted in an increased destruction rate of the carbon containing compound compared to no catalyst.

The present invention is a method and apparatus for altering a carbon-containing compound in an aqueous mixture. According to a first aspect of the present invention, it has been discovered that for an aqueous mixture having a carbon containing compound with an ozone reaction rate less than the ozone reaction rate of pentachlorophenol, use of corona discharge in a low or non-oxidizing atmosphere increases the rate of destruction of the carbon containing compound compared to corona discharge an oxidizing atmosphere. For an aqueous mixture containing pentachlorphenol, there was essentially no difference in destruction between atmospheres. According to a second aspect of the present invention, it has been further discovered that an aqueous mixture having a carbon-containing compound in the presence of a catalyst and oxygen resulted in an increased destruction rate of the carbon containing compound compared to no catalyst.

The objective of this project was to understand the importance of and the contribution of gas-phase and solid-phase coal constituents in the mercury oxidation reactions. The project involved both experimental and modeling efforts. The team was comprised of the University of Utah, Reaction Engineering International, and the University of Connecticut. The objective was to determine the experimental parameters of importance in the homogeneous and heterogeneous oxidation reactions; validate models; and, improve existing models. Parameters studied include HCl, NO{sub x}, and SO{sub 2} concentrations, ash constituents, and temperature. The results suggested that homogeneous mercury oxidation is below 10% which is not consistent with previous data of others and work which was completed early in this research program. Previous data showed oxidation above 10% and up to 100%. However, the previous data are suspect due to apparent oxidation occurring within the sampling system where hypochlorite ion forms in the KCl impinger, which in turn oxidized mercury. Initial tests with entrained iron oxide particles injected into a flame reactor suggest that iron present on fly ash particle surfaces can promote heterogeneous oxidation of mercury in the presence of HCl under entrained flow conditions. Using the data generated above, with homogeneous reactions accounting for less than 10% of the oxidation, comparisons were made to pilot- and full-scale data. The results suggest that heterogeneous reactions, as with the case of iron oxide, and adsorption on solid carbon must be taking place in the full-scale system. Modeling of mercury oxidation using parameters from the literature was conducted to further study the contribution of homogeneous pathways to Hg oxidation in coal combustion systems. Calculations from the literature used rate parameters developed in different studies, in some cases using transition state theory with a range of approaches and basis sets, and in other cases using empirical approaches. To address this, rate constants for the entire 8-step homogeneous Hg oxidation sequence were developed using an internally consistent transition state approach. These rate constants when combined with the appropriate sub-mechanisms produced lower estimates of the overall extent of homogeneous oxidation, further suggesting that heterogeneous pathways play an important role in Hg oxidation in coal-fired systems.

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

High activity steam reforming iron oxide catalysts are described. Such catalysts can be unsupported utilizing at least 90% by weight iron oxide and various modifiers (Ai/sub 2/O/sub 3/, K/sub 2/O, CaO, SiO/sub 2/) or unmodified and supported on such things as alumina, CaO impregnated alumina, and lanthanum stabilized alumina. When used in steam reformers such as autothermal and tubular steam reformers, these catalysts demonstrate much improved resistance to carbon plugging.

An article and method of producing an article for converting energy from one form to another having a pitch-derived graphitic foam carbon foam substrate and a single layer coating applied to all exposed surfaces wherein the coating is either silicon carbide or carbides formed from a Group IVA metal. The article is used as fully coated carbon foam susceptors that more effectively absorb radio frequency (RF) band energy and more effectively convert the RF energy into thermal band energy or sensible heat. The essentially non-permeable coatings also serve as corrosion or oxidation resistant barriers.

dioxide, particulate PAHs are most strongly correlated with NOx. Mexico City's PAH-to-black carbon mass and particu- late properties at six locations throughout the city. The measurements were intended to5 support of sources and15 ages of particles are present. Among carbonmonoxide, nitrogen oxides (NOx), and carbon

and carbon dioxide, and is a major source of other compounds such as carbonmonoxide (CO), volatile organic25 compounds, nitrogen oxides (NOx =NO+NO2), carbon dioxide (CO2) and organic halo- 11522 #12;ACPD 6, 11521 recognize which columns have fires. Using a land use dataset appropriate fire properties are selected

Increasing the surface acidity of active carbons can lead to an increase in capacity for hydrogen adsorption. Increasing the surface basicity can facilitate methane adsorption. The treatment of carbons is most effective when the carbon source material is selected to have a low ash content i.e., below about 3%, and where the ash consists predominantly of alkali metals alkali earth, with only minimal amounts of transition metals and silicon. The carbon is washed in water or acid and then oxidized, e.g. in a stream of oxygen and an inert gas at an elevated temperature.

A biofilter is described for reducing concentrations of gaseous nitrogen oxides in a polluted gas comprises a porous organic filter bed medium disposed in a housing, the filter bed medium including a mixed culture of naturally occurring denitrifying bacteria for converting the nitrogen oxides to nitrogen gas, carbon dioxide, and water. A method is described of reducing concentrations of nitrogen oxides in polluted gas comprises conducting the polluted gas through the biofilter so that the denitrifying bacteria can degrade the nitrogen oxides. A preferred filter medium is wood compost, however composts of other organic materials are functional. Regulation of pH, moisture content, exogenous carbon sources, and temperature are described. 6 figs.

A biofilter for reducing concentrations of gaseous nitrogen oxides in a polluted gas comprises a porous organic filter bed medium disposed in a housing, the filter bed medium including a mixed culture of naturally occurring denitrifying bacteria for converting the nitrogen oxides to nitrogen gas, carbon dioxide, and water. A method of reducing concentrations of nitrogen oxides in polluted gas comprises conducting the polluted gas through the biofilter so that the denitrifying bacteria can degrade the nitrogen oxides. A preferred filter medium is wood compost, however composts of other organic materials are functional. Regulation of pH, moisture content, exogenous carbon sources, and temperature are described.

Two new classes of catalysts for the removal of heavy metal contaminants, especially mercury (Hg) from effluent gases. Both of these classes of catalysts are excellent absorbers of HCl and Cl.sub.2 present in effluent gases. This adsorption of oxidizing agents aids in the oxidation of heavy metal contaminants. The catalysts remove mercury by oxidizing the Hg into mercury (II) moieties. For one class of catalysts, the active component is selected from the group consisting of iridium (Ir) and iridum-platinum (Ir/Pt) alloys. The Ir and Ir/Pt alloy catalysts are especially corrosion resistant. For the other class of catalyst, the active component is partially combusted coal or "Thief" carbon impregnated with Cl.sub.2. Untreated Thief carbon catalyst can be self-activating in the presence of effluent gas streams. The Thief carbon catalyst is disposable by means of capture from the effluent gas stream in a particulate collection device (PCD).

The electronic properties of polycrystalline lead oxide consisting of a network of single-crystalline $\\alpha$-PbO platelets and the formation of the native point defects in $\\alpha$-PbO crystal lattice are studied using first principles calculations. The $\\alpha$-PbO lattice consists of weakly coupled layers with inter-layer interactions of 0.013 eV/atom that is too low to produce high efficiency charge transfer between the adjacent layers. In practice, the polycrystalline nature of $\\alpha$-PbO causes the formation of lattice defects in such a high concentration that defect-related conductivity becomes the dominant factor in the interlayer charge transition. We found that the formation energy for the O vacancies is low, such vacancies are occupied by two electrons in the zero charge state and tend to donate their electrons to the Pb vacancies that leads to ionization of both vacancies.The vacancies introduce localized states in the band gap which can affect charge transport. The O vacancy forms a defect sta...

of the graphene sheets comprising the carbon nanofibers. Over oxidation of the edges or their removal by heat of the graphene sheets of the support. A mechanism for DEC synthesis is discussed, and a role for the Pd2+ cations

This Final Report contains the test descriptions, results, analysis, correlations, theoretical descriptions, and model derivations produced from many different investigations performed on a project funded by the U.S. Department of Energy, to investigate calcium-based sorbents and injection of oxidizing agents for the removal of mercury. Among the technologies were (a) calcium-based sorbents in general, (b) oxidant-additive sorbents developed originally at the EPA, and (c) optimized calcium/carbon synergism for mercury-removal enhancement. In addition, (d) sodium-tetrasulfide injection was found to effectively capture both forms of mercury across baghouses and ESPs, and has since been demonstrated at a slipstream treating PRB coal. It has been shown that sodium-tetrasulfide had little impact on the foam index of PRB flyash, which may indicate that sodium-tetrasulfide injection could be used at power plants without affecting flyash sales. Another technology, (e) coal blending, was shown to be an effective means of increasing mercury removal, by optimizing the concentration of calcium and carbon in the flyash. In addition to the investigation and validation of multiple mercury-control technologies (a through e above), important fundamental mechanism governing mercury kinetics in flue gas were elucidated. For example, it was shown, for the range of chlorine and unburned-carbon (UBC) concentrations in coal-fired utilities, that chlorine has much less effect on mercury oxidation and removal than UBC in the flyash. Unburned carbon enhances mercury oxidation in the flue gas by reacting with HCl to form chlorinated-carbon sites, which then react with elemental mercury to form mercuric chloride, which subsequently desorbs back into the flue gas. Calcium was found to enhance mercury removal by stabilizing the oxidized mercury formed on carbon surfaces. Finally, a model was developed to describe these mercury adsorption, desorption, oxidation, and removal mechanisms, including the synergistic enhancement of mercury removal by calcium.

Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. Oxide catalysis can be a complex process with both metal cation and oxygen anions participating in the chemical reactions. From an energy perspective carbon-carbon bond formation is particularly relevant to CO hydrogenation in isosynthesis. Hydrogenolysis and hydrogenation form the basis for heteroatom removal in fuels processing. Understanding the catalysis of these processes (and others) requires isolating reaction steps in the overall cycle and determining how structure and composition influence the individual reaction steps. Specially designed oxides, such as we use, permit one to study some of the steps in oxidation, carbon-carbon coupling and heteroatom removal catalysis. During the course of our studies we have: (1) developed methods to form and stabilize various Mo and W oxide structures on silica; (2) studied C-H abstraction reactions over the fully oxidized cations; (3) studied C-C bond coupling by methathesis and reductive coupling of aldehydes and ketones over reduced cation structures; and (4) initiated a study of hydrogenation and hydrogenolysis over reduced cation structures.

Silicon-containing solvents have tremendous potential for application as electrolytes for electrical energy storage devices such as lithium-ion (air) batteries and supercapacitors. Quantum chemical methods were employed to investigate trends in oxidation potentials and decomposition reactions of a series of polysiloxanes. Various electron-donating and -withdrawing substituents can be used to tune the oxidation potential in shorter chain siloxanes but not in longer ones. Decomposition reactions of siloxanes in their oxidized states were investigated and compared against their carbon analogues. These studies suggest that the Si-O group provides added stability for siloxanes over their carbon analogues. Computational studies have also been performed for various disiloxanes and siloxanes with spacer groups to understand their thermochemical stability and oxidation potentials.

Laboratory measurements of mercury oxidation during selective catalytic reduction (SCR) of nitric oxide, simulation of pilot-scale measurements of mercury oxidation and adsorption by unburned carbon and fly ash, and synthesis of new materials for simultaneous oxidation and adsorption of mercury, were performed in support of the development of technology for control of mercury emissions from coal-fired boilers and furnaces. Conversion of gas-phase mercury from the elemental state to water-soluble oxidized form (HgCl{sub 2}) enables removal of mercury during wet flue gas desulfurization. The increase in mercury oxidation in a monolithic V{sub 2}O{sub 5}-WO{sub 3}/TiO{sub 2} SCR catalyst with increasing HCl at low levels of HCl (< 10 ppmv) and decrease in mercury oxidation with increasing NH{sub 3}/NO ratio during SCR were consistent with results of previous work by others. The most significant finding of the present work was the inhibition of mercury oxidation in the presence of CO during SCR of NO at low levels of HCl. In the presence of 2 ppmv HCl, expected in combustion products from some Powder River Basin coals, an increase in CO from 0 to 50 ppmv reduced the extent of mercury oxidation from 24 {+-} 3 to 1 {+-} 4%. Further increase in CO to 100 ppmv completely suppressed mercury oxidation. In the presence of 11-12 ppmv HCl, increasing CO from 0 to {approx}120 ppmv reduced mercury oxidation from {approx}70% to 50%. Conversion of SO{sub 2} to sulfate also decreased with increasing NH{sub 3}/NO ratio, but the effects of HCl and CO in flue gas on SO{sub 2} oxidation were unclear. Oxidation and adsorption of mercury by unburned carbon and fly ash enables mercury removal in a particulate control device. A chemical kinetic mechanism consisting of nine homogeneous and heterogeneous reactions for mercury oxidation and removal was developed to interpret pilot-scale measurements of mercury oxidation and adsorption by unburned carbon and fly ash in experiments at pilot scale, burning bituminous coals (Gale, 2006) and blends of bituminous coals with Powder River Basin coal (Gale, 2005). The removal of mercury by fly ash and unburned carbon in the flue gas from combustion of the bituminous coals and blends was reproduced with satisfactory accuracy by the model. The enhancement of mercury capture in the presence of calcium (Gale, 2005) explained a synergistic effect of blending on mercury removal across the baghouse. The extent of mercury oxidation, on the other hand, was not so well described by the simulation, because of oversensitivity of the oxidation process in the model to the concentration of unburned carbon. Combined catalysts and sorbents for oxidation and removal of mercury from flue gas at low temperature were based on surfactant-templated silicas containing a transition metal and an organic functional group. The presence of both metal ions and organic groups within the pore structure of the materials is expected to impart to them the ability to simultaneously oxidize elemental mercury and adsorb the resulting oxidized mercury. Twelve mesoporous organosilicate catalysts/sorbents were synthesized, with and without metals (manganese, titanium, vanadium) and organic functional groups (aminopropyl, chloropropyl, mercaptopropyl). Measurement of mercury oxidation and adsorption by the candidate materials remains for future work.

Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

A method of carbonmonoxide (CO) removal comprises providing an oxidation catalyst comprising cobalt supported on an inorganic oxide. The method further comprises feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to the catalyst system, and removing CO from the gaseous stream by oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of the oxidation catalyst at a temperature between about 20 to about 200.degree. C.

Transition metal complexes of meso-haloalkylporphyrins are disclosed, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

The kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) on polycrystalline platinum [Pt(pc)] and high surface area carbon-supported platinum nanoparticles (Pt/C) were studied in 0.1 M ...

CALIFORNIA ENERGY COMMISSION CARBON SEQUESTRATION THROUGH CHANGES IN LAND USE IN WASHINGTON. Carbon Sequestration Through Changes in Land Use in Washington: Costs and Opportunities. California for Terrestrial Carbon Sequestration in Oregon. Report to Winrock International. #12;ii #12;iii Preface

This thesis reviews the recent advances made in optical studies of single-wall carbon nanotubes. Studying the electronic and vibrational properties of carbon nanotubes, we find that carbon nanotubes less than 1 nm in ...

Catalysis is the key fundamental ingredient to convert elemental mercury in coal-fired power stations into its oxidized forms that are more easily captured by sorbents, ESPs, baghouses, and wet scrubbers, whether the catalyst be unburned carbon (UBC) in the ash or vanadium pentoxide in SCR catalysts. This project has investigated several different types of catalysts that enhance mercury oxidation in several different ways. The stated objective of this project in the Statement of Objectives included testing duct-injection catalysts, catalyst-sorbent hybrids, and coated low-pressure-drop screens. Several different types of catalysts were considered for duct injection, including different forms of iron and carbon. Duct-injection catalysts would have to be inexpensive catalysts, as they would not be recycled. Iron and calcium had been shown to catalyze mercury oxidation in published bench-scale tests. However, as determined from results of an on-going EPRI/EPA project at Southern Research, while iron and calcium did catalyze mercury oxidation, the activity of these catalysts was orders of magnitude below that of carbon and had little impact in the short residence times available for duct-injected catalysts or catalyst-sorbent hybrids. In fact, the only catalyst found to be effective enough for duct injection was carbon, which is also used to capture mercury and remove it from the flue gas. It was discovered that carbon itself is an effective catalyst-sorbent hybrid. Bench-scale carbon-catalyst tests were conducted, to obtain kinetic rates of mercury adsorption (a key step in the catalytic oxidation of mercury by carbon) for different forms of carbon. All carbon types investigated behaved in a similar manner with respect to mercury sorption, including the effect of temperature and chlorine concentration. Activated carbon was more effective at adsorbing mercury than carbon black and unburned carbon (UBC), because their internal surface area of activated carbon was greater. Catalyst coating of low-pressure-drop screens was of particular interest as this project was being developed. However, it was discovered that URS was already heavily involved in the pursuit of this same technology, being funded by DOE, and reporting significant success. Hence, testing of SCR catalysts became a major focus of the project. Three different commercial SCR catalysts were examined for their ability to oxidize mercury in simulated flue-gas. Similar performance was observed from each of the three commercial catalysts, both in terms of mercury oxidation and SO{sub 3} generation. Ammonia injection hindered mercury oxidation at low HCl concentrations (i.e., {approx}2 ppmv), yet had little impact on mercury oxidation at higher HCl concentrations. On the other hand, SO{sub 2} oxidation was significantly reduced by the presence of ammonia at both low and high concentrations of HCl.

Free-standing paper-like or foil-like materials are an integral part of our technological society. Their uses include protective layers, chemical filters, components of electrical batteries or supercapacitors, adhesive layers, electronic or optoelectronic components, and molecular storage. Inorganic 'paper-like' materials based on nanoscale components such as exfoliated vermiculite or mica platelets have been intensively studied and commercialized as protective coatings, high-temperature binders, dielectric barriers and gas-impermeable membranes. Carbon-based flexible graphite foils composed of stacked platelets of expanded graphite have long been used in packing and gasketing applications because of their chemical resistivity against most media, superior sealability over a wide temperature range, and impermeability to fluids. The discovery of carbon nanotubes brought about bucky paper, which displays excellent mechanical and electrical properties that make it potentially suitable for fuel cell and structural composite applications. Here we report the preparation and characterization of graphene oxide paper, a free-standing carbon-based membrane material made by flow-directed assembly of individual graphene oxide sheets. This new material outperforms many other paper-like materials in stiffness and strength. Its combination of macroscopic flexibility and stiffness is a result of a unique interlocking-tile arrangement of the nanoscale graphene oxide sheets.

A titanium silicide material based on Ti.sub.5 Si.sub.3 intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000.degree. C. Boron is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end.

A titanium silicide material based on Ti.sub.5 Si.sub.3 intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000.degree. C. Boron is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end.

A titanium silicide material based on Ti.sub.5 Si.sub.3 intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000.degree. C. Boron is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end.

The experiment investigated effects of high quantities of manganese and route of administration (diet versus capsule-dosed) on feed intake and blood characteristics in sheep. Twenty-four Florida native or Florida native by St. Croix crossbred wethers, 47 kg initially, were assigned randomly to eight treatments including basal diet supplemented with 0, 3000, 6000, or 9000 ppm manganese as a reagent grade manganese monoxide or basal diet plus gelatin capsules containing the equivalent of 0, 3000, 6000, or 9000 ppm manganese based on intake of the previous day. Three sheep per treatment were provided feed and tap water for ad libitum intake. Sheep were fed basal diet for 7 days followed by a 21-day experimental period, then placed back on the basal diet for 7 days. Average daily feed intake was reduced by increasing supplemental manganese, regardless of route. Animals dosed by capsule consumed less feed than those administered manganese in the diet. Serum manganese increased as manganese supplementation increased, but route of administration had no effect.

A process for making 2D and 3D carbon-carbon composites having a combined high crystallinity, high strength, high modulus and high thermal and electrical conductivity. High-modulus/high-strength mesophase derived carbon fibers are woven into a suitable cloth. Layers of this easily graphitizible woven cloth are infiltrated with carbon material to form green composites. The carbonized composite is then impregnated several times with pitch by covering the composite with hot pitch under pressure. The composites are given a heat treatment between each impregnant step to crack up the infiltrated carbon and allow additional pitch to enter the microstructure during the next impregnation cycle. The impregnated composites are then given a final heat treatment in the range 2500.degree. to 3100.degree. C. to fully graphitize the fibers and the matrix carbon. The composites are then infiltrated with pyrolytic carbon by chemical vapor deposition in the range 1000.degree. C. to 1300.degree. C. at a reduced. pressure.

A process for water oxidation of combustible materials in which during at least a part of the oxidation corrosive material is present and makes contact with at least a portion of the apparatus over a contact area on the apparatus. At least a portion of the contact surface area comprises titanium dioxide coated onto a titanium metal substrate. Such ceramic composites have been found to be highly resistant to environments encountered in the process of supercritical water oxidation. Such environments typically contain greater than 50 mole percent water, together with oxygen, carbon dioxide, and a wide range of acids, bases, and salts. Pressures are typically about 27.5 to about 1000 bar while temperatures range as high as 700.degree. C. The ceramic composites are also resistant to degradation mechanisms caused by thermal stresses.

Berend Smit speaks at the Carbon Cycle 2.0 kick-off symposium Feb. 3, 2010. We emit more carbon into the atmosphere than natural processes are able to remove - an imbalance with negative consequences. Carbon Cycle 2.0 is a Berkeley Lab initiative to provide the science needed to restore this balance by integrating the Labs diverse research activities and delivering creative solutions toward a carbon-neutral energy future. http://carboncycle2.lbl.gov/

A process for making carbon film or powder suitable for double capacitor electrodes having a capacitance of up to about 300 F/cm.sup.3 is disclosed. This is accomplished by treating in aqueous nitric acid for a period of about 5 to 15 minutes thin carbon films obtained by carbonizingcarbon-containing polymeric material having a high degree of molecular directionality, such as polyimide film, then heating the treated carbon film in a non-oxidizing atmosphere at a non-graphitizing temperature of at least 350.degree. C. for about 20 minutes, and repeating alternately the nitric acid step and the heating step from 7 to 10 times. Capacitors made with this carbon may find uses ranging from electronic devices to electric vehicle applications.

results were obtained using an asbestos supported CuO-Cr203 catalyst. Venkataramam and his co-workers (66) studied the catalytic oxidation of ethylene to ethylene oxide by the fluidized bed technique using a static bed of catalyst. Precipitated Ag20... in the air-ethylene ratio to maintain good yields of ethylene oxide. Wan (68) reported the oxidation of ethylene to acetaldehyde by use of a silver catalyst in a 5/16 dnch inner diameter stainless steel tube with a catalyst bed up to 30. 3 centimeters...

The combustion of coal by wet oxidation was studied by the Center for Waste Management Programs, of Michigan Technological University. In wet oxidation a combustible material, such as coal, is reacted with oxygen in the presence of liquid water. The reaction is typically carried out in the range of 204/sup 0/C (400/sup 0/F) to 353/sup 0/C (650/sup 0/F) with sufficient pressure to maintain the water present in the liquid state, and provide the partial pressure of oxygen in the gas phase necessary to carry out the reaction. Experimental studies to explore the key reaction parameters of temperature, time, oxidant, catalyst, coal type, and mesh size were conducted by running batch tests in a one-gallon stirred autoclave. The factors exhibiting the greatest effect on the extent of reaction were temperature and residence time. The effect of temperature was studied from 204/sup 0/C (400/sup 0/F) to 260/sup 0/C (500/sup 0/F) with a residence time from 600 to 3600 seconds. From this data, the reaction activation energy of 2.7 x 10/sup 4/ calories per mole was determined for a high-volatile-A-Bituminous type coal. The reaction rate constant may be determined at any temperature from the activation energy using the Arrhenius equation. Additional data were generated on the effect of mesh size and different coal types. A sample of peat was also tested. Two catalysts were evaluated, and their effects on reaction rate presented in the report. In addition to the high temperature combustion, low temperature desulfurization is discussed. Desulfurization can improve low grade coal to be used in conventional combustion methods. It was found that 90% of the sulfur can be removed from the coal by wet oxidation with the carbon untouched. Further desulfurization studies are indicated.

Carbon aerogels used as a binder for granulated materials, including other forms of carbon and metal additives, are cast onto carbon or metal fiber substrates to form composite carbon thin film sheets. The thin film sheets are utilized in electrochemical energy storage applications, such as electrochemical double layer capacitors (aerocapacitors), lithium based battery insertion electrodes, fuel cell electrodes, and electrocapacitive deionization electrodes. The composite carbon foam may be formed by prior known processes, but with the solid particles being added during the liquid phase of the process, i.e. prior to gelation. The other forms of carbon may include carbon microspheres, carbon powder, carbon aerogel powder or particles, graphite carbons. Metal and/or carbon fibers may be added for increased conductivity. The choice of materials and fibers will depend on the electrolyte used and the relative trade off of system resistivity and power to system energy. 1 fig.

Carbon aerogels used as a binder for granularized materials, including other forms of carbon and metal additives, are cast onto carbon or metal fiber substrates to form composite carbon thin film sheets. The thin film sheets are utilized in electrochemical energy storage applications, such as electrochemical double layer capacitors (aerocapacitors), lithium based battery insertion electrodes, fuel cell electrodes, and electrocapacitive deionization electrodes. The composite carbon foam may be formed by prior known processes, but with the solid particles being added during the liquid phase of the process, i.e. prior to gelation. The other forms of carbon may include carbon microspheres, carbon powder, carbon aerogel powder or particles, graphite carbons. Metal and/or carbon fibers may be added for increased conductivity. The choice of materials and fibers will depend on the electrolyte used and the relative trade off of system resistivty and power to system energy.

We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbonmonoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75?ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir–C and Ir–Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule.

and infrared spectroscopy. It was found to consist mainly of a solid solution of calcium sulfate and calcium sulfite hemihydrate, calcium sulfate dihydrate and unreacted calcium carbonate. 1 Pure CaSO3. ? H20 was synthesized as a model and was used... in slurries containing I to 12 % of solids in the temperature range 40 to 70 'C, using sulfuric acid to control the pH and to convert calcium carbonate to calcium sulfate dihydrate. Air and hydrogen peroxide were used as the oxidizing agents. When air...

Carbon aerogels offer several unique advantages which make them ideal for evaluating a metal's ability to catalyze nanotube growth, including in situ carbothermic reduction of oxidized nanoparticles to their catalytic ...

Efficient and scalable solution-based processes are not generally available to integrate well-studied pseudocapacitive materials (i.e., metal oxides and conducting polymers) with other components such as porous carbon, ...

The tungsten carbonyl species that form during ultraviolet photoreduction of W[sup 6+]SiO[sub 2] in CO were analyzed by Fourier transform infrared spectroscopy (FTIR). Two carbonyl species were identified, mer-W(CO)[sub 3] and cis-W(CO)[sub 2], by the number and intensities of the respective IR peaks and through isotopic substitution. The C[sub 2v] symmetry of mer-W(CO)[sub 3] was associated with three IR bands: a very weak (A[sub 1])[sub 1] symmetric trans mode at 2145 cm[sup [minus]1], a strong B[sub 2] symmetric mode at 2112 cm[sup [minus]1], and a strong (A[sub 1])[sub 2] antisymmetric mode at 2179 cm[sup [minus]1] mer-W(CO)[sub 3] was stable at 298 K in 25 Torr of CO. Isothermal evacuation of the mer-W(CO)[sub 3] species resulted in the loss of a single CO ligand, forming cis-W(CO)[sub 2]. The W(CO)[sub 2] species formed during both isothermal evacuation of the mer-W(CO)[sub 3] species and during the initial photoreduction process. cis-W(CO)[sub 2] was identified by its IR spectrum consisting of a strong symmetric mode at 2112 cm[sup [minus]1] and a strong antisymmetric mode at 2040 cm[sup [minus]1]. 22 refs., 9 figs., 2 tabs.

at the InterTropical Convergence Zone (ITCZ). The marked tracer study suggests that biofuel use the globe where biofuel use and biomass burning contribute so much to the CO mixing ratios. In general, most is the dominant CO source at middle and high northern latitudes, whereas biofuel use and biomass burning are major

and water heaters, stoves and other gasoline pow- ered equipment used in households. Typically, CO levels of 0.5Â­5 ppm are expected in homes in the absence of high-efficiency heaters and stoves. In spaces where gas stoves/heaters are operated, the CO concentration can increase up to 30 ppm [6]. In this work

of the quality assurance of emissions reduction and carbon sequestration activities, but remains a source of muchResearch Summary Carbon Additionality Additionality is widely considered to be a core aspect controversy in national carbon accounting, international regulatory frameworks and carbon markets. A review

A fourth allotrope of carbon, an acetylenic carbon allotrope, is described. The acetylenic carbon allotropes of the present invention are more soluble than the other known carbon allotropes in many common organic solvents and possesses other desirable characteristics, e.g. high electron density, ability to burn cleanly, and electrical conductive properties. Many uses for this fourth allotrope are described herein. 17 figs.

The Woodland Carbon Code While society must continue to make every effort to reduce greenhouse gas a role by removing carbon dioxide from the atmosphere. The potential of woodlands to soak up carbon to help compensate for their carbon emissions. But before investing in such projects, people want to know

Stabilized quadrivalent cation oxide electrolytes are employed in fuel cells at elevated temperatures with a carbon and/or hydrogen containing fuel anode and an oxygen cathode. The fuel cell is operated at elevated temperatures with conductive metallic coatings as electrodes and desirably having the electrolyte surface blackened. Of particular interest as the quadrivalent oxide is zirconia.

A conductive mesoporous carbon composite comprising conductive carbon nanoparticles contained within a mesoporous carbon matrix, wherein the conductive mesoporous carbon composite possesses at least a portion of mesopores having a pore size of at least 10 nm and up to 50 nm, and wherein the mesopores are either within the mesoporous carbon matrix, or are spacings delineated by surfaces of said conductive carbon nanoparticles when said conductive carbon nanoparticles are fused with each other, or both. Methods for producing the above-described composite, devices incorporating them (e.g., lithium batteries), and methods of using them, are also described.

The disclosure relates a niobium oxide useful in anodes of secondary lithium ion batteries. Such niobium oxide has formula Li.sub.xM.sub.1-yNb.sub.yNb.sub.2O.sub.7, wherein 0.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.1, and M represents Ti or Zr. The niobium oxide may be in the form of particles, which may be carbon coated. The disclosure also relates to an electrode composition containing at least one or more niobium oxides of formula Li.sub.xM.sub.1-yNb.sub.yNb.sub.2O.sub.7. The disclosure further relates to electrodes, such as anodes, and batteries containing at least one or more niobium oxides of formula Li.sub.xM.sub.1-yNb.sub.yNb.sub.2O.sub.7. Furthermore, the disclosure relates to methods of forming the above.

Graphite is a fundamental material of high temperature gas cooled nuclear reactors, providing both structure and neutron moderation. Its high thermal conductivity, chemical inertness, thermal heat capacity, and high thermal structural stability under normal and off normal conditions contribute to the inherent safety of these reactor designs. One of the primary safety issues for a high temperature graphite reactor core is the possibility of rapid oxidation of the carbon structure during an off normal design basis event where an oxidizing atmosphere (air ingress) can be introduced to the hot core. Although the current Generation IV high temperature reactor designs attempt to mitigate any damage caused by a postualed air ingress event, the use of graphite components that inhibit oxidation is a logical step to increase the safety of these reactors. Recent experimental studies of graphite containing between 5.5 and 7 wt% boron carbide (B4C) indicate that oxidation is dramatically reduced even at prolonged exposures at temperatures up to 900°C. The proposed addition of B4C to graphite components in the nuclear core would necessarily be enriched in B-11 isotope in order to minimize B-10 neutron absorption and graphite swelling. The enriched boron can be added to the graphite during billet fabrication. Experimental oxidation rate results and potential applications for borated graphite in nuclear reactor components will be discussed.

This invention pertains to a high temperature, ceramic composition having electronic conductivity as measured by resistivity below about 500 ohm-cm, chemical stability particularly with respect to cathode conditions in a molten carbonate fuel cell, and composed of an alkali metal, transition metal oxide containing a dopant metal in the crystalline structure to replace a portion of the alkali metal or transition metal.

The objective of this program is to fabricate and test oxide fiber reinforced composite hot gas filter elements for advanced power generation systems. The level of mechanical durability exhibited by the currently available filters in field tests indicates that more rugged filters are required to meet the demands of large power generation systems. Furthermore, long term corrosion resistance of currently available filters has yet to be demonstrated in PFBC systems. The essential requirements of a composite material designed to meet the program objective for a toughened hot gas filter include the following: Stable continuous fiber; rigid porous matrix; engineered fiber-matrix interface; and cost effectiveness. Based on properties, availability, and cost, Mitsui`s ALMAX alumina fiber and 3M`s NEXTEL 610 alumina fiber were selected as the oxide reinforcement fibers. In order to meet the economic goals of the program it is essential that the cost and amount of continuous fiber be minimized. A four axis filament winder will be used to fabricate filter Preforms in a variety of fiber architectures. Carbon was used as the initial fiber coating because it was known to be resistant to the Processing chemicals. The coating was produced by pyrolysis of the resin based sizings on the continuous fibers. The matrix of the composite filter is comprised of chopped ceramic fiber. Saffil fiber was used for all compositions in this program.

A method is disclosed for preparing a dimensionally stable electrode structure, particularly nickel-chromium anodes, for use in a molten carbonate fuel cell stack. A low-chromium to nickel alloy is provided and oxidized in a mildly oxidizing gas of sufficient oxidation potential to oxidize chromium in the alloy structure. Typically, a steam/H/sub 2/ gas mixture in a ratio of about 100/1 and at a temperature below 800/sup 0/C is used as the oxidizing medium. This method permits the use of less than 5 wt % chromium in nickel alloy electrodes while obtaining good resistance to creep in the electrodes of a fuel cell stack.

Methods and systems are provided for producing syngas utilizing heat from thermochemical conversion of a carbonaceous fuel to support decomposition of at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells. Simultaneous decomposition of carbon dioxide and water or steam by one or more solid-oxide electrolysis cells may be employed to produce hydrogen and carbonmonoxide. A portion of oxygen produced from at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells is fed at a controlled flow rate in a gasifier or combustor to oxidize the carbonaceous fuel to control the carbon dioxide to carbonmonoxide ratio produced.

Hydrogen generator coupled to or integrated with a fuel cell for portable power applications. Hydrogen is produced via thermocatalytic decomposition (cracking, pyrolysis) of hydrocarbon fuels in oxidant-free environment. The apparatus can utilize a variety of hydrocarbon fuels, including natural gas, propane, gasoline, kerosene, diesel fuel, crude oil (including sulfurous fuels). The hydrogen-rich gas produced is free of carbonoxides or other reactive impurities, so it could be directly fed to any type of a fuel cell. The catalysts for hydrogen production in the apparatus are carbon-based or metal-based materials and doped, if necessary, with a sulfur-capturing agent. Additionally disclosed are two novel processes for the production of two types of carbon filaments, and a novel filamentous carbon product. Carbon particles with surface filaments having a hydrophobic property of oil film absorption, compositions of matter containing those particles, and a system for using the carbon particles for cleaning oil spills.

Tropospheric ozone reduces carbon assimilation in trees: estimates from analysis of continuous flux Abstract High ground-level ozone concentrations are typical of Mediterranean climates. Plant exposure to this oxidant is known to reduce carbon assimilation. Ozone damage has been traditionally measured through

. Virgin carbon and carbon modified by oxidation with HNO3, NaOH and H2O2 were examined in this study for their ability to remove perchlorate by reduction or adsorption mechanisms. Surface functional groups formed on the modified AC (MAC) were examined...

An electrochemical cell apparatus that can operate as either a fuel cell or a battery includes a cathode compartment, an anode compartment operatively connected to the cathode compartment, and a carbon fuel cell section connected to the anode compartment and the cathode compartment. An effusion plate is operatively positioned adjacent the anode compartment or the cathode compartment. The effusion plate allows passage of carbon dioxide. Carbon dioxide exhaust channels are operatively positioned in the electrochemical cell to direct the carbon dioxide from the electrochemical cell.

A method and article of manufacture of amorphous diamond-like carbon. The method involves providing a substrate in a chamber, providing a mixture of a carbon containing gas and hydrogen gas with the mixture adjusted such that the atomic molar ratio of carbon to hydrogen is less than 0.3, including all carbon atoms and all hydrogen atoms in the mixture. A plasma is formed of the mixture and the amorphous diamond-like carbon film is deposited on the substrate. To achieve optimum bonding an intervening bonding layer, such as Si or SiO.sub.2, can be formed from SiH.sub.4 with or without oxidation of the layer formed.

A method of providing an exhaust treatment device is disclosed. The method includes applying a catalyst including gold and a platinum group metal to a particulate filter. The concentration of the gold and the platinum group metal is sufficient to enable oxidation of carbonmonoxide and nitric oxide.

A method and apparatus for the destruction of emissions from an internal combustion engine wherein a substrate coated with TiO.sub.2 is exposed to a light source in the exhaust system of an internal combustion engine thereby catalyzing oxidation/reduction reactions between gaseous hydrocarbons, carbonmonoxide, nitrogen oxides and oxygen in the exhaust of the internal combustion engine.

The Very High Temperature Reactor (VHTR) Graphite Research and Development Program is investigating doped nuclear graphite grades exhibiting oxidation resistance. During a oxygen ingress accident the oxidation rates of the high temperature graphite core region would be extremely high resulting in significant structural damage to the core. Reducing the oxidation rate of the graphite core material would reduce the structural effects and keep the core integrity intact during any air-ingress accident. Oxidation testing of graphite doped with oxidation resistant material is being conducted to determine the extent of oxidation rate reduction. Nuclear grade graphite doped with varying levels of Boron-Carbide (B4C) was oxidized in air at nominal 740°C at 10/90% (air/He) and 100% air. The oxidation rates of the boronated and unboronated graphite grade were compared. With increasing boron-carbide content (up to 6 vol%) the oxidation rate was observed to have a 20 fold reduction from unboronated graphite. Visual inspection and uniformity of oxidation across the surface of the specimens were conducted. Future work to determine the remaining mechanical strength as well as graphite grades with SiC doped material are discussed.

Lignin-based carbons can be used as a low-cost alternative to graphite and petroleum-based carbons enabling the production of sustainable, functional carbon materials for various applications. The microstructure development of these carbons can be controlled through chemical modification of the lignin precursor and choice of carbonization parameters. In this work, microstructured carbon materials are synthesized from lignin using a combination of chemical modification and carbon fiber processing techniques. Lignin is modified by incorporating different ester groups which results in a precursor highly compatible with melt processing using the fiber extrusion technique and conversion into microstructured carbons by oxidative stabilization and subsequent carbonization. Furthermore, the impact of esterifications on precursor chemistry and carbonizations is investigated. A nuclear magnetic resonance study of modified lignins shows characteristic spectral changes as a result of esterifications. Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry shows the modification process does not affect the polymeric character of the lignin backbone. Esterifications result in moderate shifts in O:C and H:C ratios. Thermogravimetric analysis of lignins reveals distinct differences in mass loss trends during oxidations and carbonizations.

This chapter covers the fundamental science, synthesis, characterization, physicochemical properties and applications of oxide nanomaterials. Explains fundamental aspects that determine the growth and behavior of these systems, briefly examines synthetic procedures using bottom-up and top-down fabrication technologies, discusses the sophisticated experimental techniques and state of the art theory results used to characterize the physico-chemical properties of oxide solids and describe the current knowledge concerning key oxide materials with important technological applications.

NETL's Carbon Sequestration Program is helping to develop technologies to capture, purify, and store carbon dioxide (CO2) in order to reduce greenhouse gas emissions without adversely influencing energy use or hindering economic growth. Carbon sequestration technologies capture and store CO2 that would otherwise reside in the atmosphere for long periods of time.

NETL's Carbon Sequestration Program is helping to develop technologies to capture, purify, and store carbon dioxide (CO2) in order to reduce greenhouse gas emissions without adversely influencing energy use or hindering economic growth. Carbon sequestration technologies capture and store CO2 that would otherwise reside in the atmosphere for long periods of time.

A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

We compare the oxidation characteristics of four different diesel particulates generated with a modern light-duty engine. The four particulates represent engine fueling with conventional ultra-low sulfur diesel (ULSD), biodiesel, and two intermediate blends of these fuels. The comparisons discussed here are based on complementary measurements implemented in a laboratory micro-reactor, including temperature programmed desorption and oxidation, pulsed isothermal oxidation, and BET surface area. From these measurements we have derived models that are consistent with the observed oxidation reactivity differences. When accessible surface area effects are properly accounted for, the oxidation kinetics of the fixed carbon components were found to consistently exhibit an Arrhenius activation energy of 113 6 kJ/mol. Release of volatile carbon from the as-collected particulate appears to follow a temperaturedependent rate law.

The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

A gasification process of improved efficiency is disclosed. A dual bed reactor system is used in which carbon-containing feedstock materials are first treated in a gasification reactor to form pyrolysis gases. The pyrolysis gases are then directed into a catalytic reactor for the destruction of residual tars/oils in the gases. Temperatures are maintained within the catalytic reactor at a level sufficient to crack the tars/oils in the gases, while avoiding thermal breakdown of the catalysts. In order to minimize problems associated with the deposition of carbon-containing materials on the catalysts during cracking, a gaseous oxidizing agent preferably consisting of air, oxygen, steam, and/or mixtures thereof is introduced into the catalytic reactor at a high flow rate in a direction perpendicular to the longitudinal axis of the reactor. This oxidizes any carbon deposits on the catalysts, which would normally cause catalyst deactivation.

A system to continuously produce fully carbonized or graphitized carbon fibers using microwave-assisted plasma (MAP) processing comprises an elongated chamber in which a microwave plasma is excited in a selected gas atmosphere. Fiber is drawn continuously through the chamber, entering and exiting through openings designed to minimize in-leakage of air. There is a gradient of microwave power within the chamber with generally higher power near where the fiber exits and lower power near where the fiber enters. Polyacrylonitrile (PAN), pitch, or any other suitable organic/polymeric precursor fibers can be used as a feedstock for the inventive system. Oxidized or partially oxidized PAN or pitch or other polymeric fiber precursors are run continuously through a MAP reactor in an inert, non-oxidizing atmosphere to heat the fibers, drive off the unwanted elements such as oxygen, nitrogen, and hydrogen, and produce carbon or graphite fibers faster than conventionally produced carbon fibers.

The objective of this paper is to investigate the transport of uranium oxide particles that may be present in carbon dioxide (CO2) gas coolant, into the graphite blocks of gas-cooled, graphite moderated reactors. The transport of uranium oxide in the coolant system, and subsequent deposition of this material in the graphite, of such reactors is of interest because it has the potential to influence the application of the Graphite Isotope Ratio Method (GIRM). The GIRM is a technology that has been developed to validate the declared operation of graphite moderated reactors. GIRM exploits isotopic ratio changes that occur in the impurity elements present in the graphite to infer cumulative exposure and hence the reactor’s lifetime cumulative plutonium production. Reference Gesh, et. al., for a more complete discussion on the GIRM technology.

One-carbon (C-1) compounds play a central role in microbial metabolism. C-1 compounds include methane, carbonmonoxide, CO2, and methanol as well as coenzyme-bound one-carbon compounds (methyl-B12, CH3-H4folate, etc). Such compounds are of broad global importance because several C-1 compounds (e.g., CH4) are important energy sources, some (e.g., CO2 and CH4) are potent greenhouse gases, and others (e.g., CH2Cl2) are xenobiotics. They are central in pathways of energy metabolism and carbon fixation by microbes and many are of industrial interest. Research on the pathways of one-carbon metabolism has added greatly to our understanding of evolution, structural biology, enzyme mechanisms, gene regulation, ecology, and applied biology. The 2008 meeting will include recent important findings in the following areas: (a) genomics, metagenomics, and proteomic studies that have expanded our understanding of autotrophy and C-1 metabolism and the evolution of these pathways; (b) redox regulation of carbon cycles and the interrelationship between the carbon cycle and other biogeochemical cycles (sulfur, nitrogen, oxygen); (c) novel pathways for carbon assimilation; (d) biotechnology related to C-1 metabolism; (e) novel enzyme mechanisms including channeling of C-1 intermediates during metabolism; and (f) the relationship between metal homeostasis and the global carbon cycle. The conference has a diverse and gender-balanced slate of speakers and session leaders. The wide variety of disciplines brought to the study of C-1 metabolism make the field an excellent one in which to train young researchers.

We consider the formation of dwarf carbon stars via accretion from a carbon AGB companion in light of the new 107 object sample of Downes et al. (2004). This sample is now large enough to allow good mass determination via comparison of a composite spectrum to theoretical atmospheric models. Carbon dwarfs of spectral type M are indeed main sequence M dwarfs with enhanced metallicity and carbon abundance. We also calculate the predicted abundance of both M and of F/G carbon dwarfs, and show that the latter should be falsifiable in the near future.

The objective of this research is the selective oxidative coupling of methane to C{sub 2}H{sub 4} hydrocarbons and oxygenates, in particular formaldehyde and methanol. Air, oxygen or carbon dioxide, rather than nitrous oxide will be utilized as the oxidizing gas at high gas hourly space velocity, but mild reaction conditions (500-700 {degrees}C, 1 atm total pressure). All the investigated processes are catalytic, aiming at minimizing gas phase reactions that are difficult to control. The research is divided into the following three tasks: (1) maximizing selective methane oxidation to C{sub 2}H{sub 4} products over promoted Sr/La{sub 2}O{sub 3}; (2) selective methane oxidation to oxygenates; and (3) catalyst characterization and optimization. Task 1 dealt with the preparation, testing, and optimization of acidic promoted lanthana-based catalysts for the synthesis of C{sub 2}H{sub 4} hydrocarbons and is essentially completed. Task 2 aims at the formation and optimization of promoted catalysts for the synthesis of oxygenates, in particular formaldehyde and methanol. Task 3 involves characterization of the most promising catalysts so that optimization can be achieved under Task 2. Accomplishments for this period are presented.

The formation of sulfur-bearing molecules in interstellar ices was investigated during the irradiation of carbon disulfide (CS{sub 2})-oxygen (O{sub 2}) ices with energetic electrons at 12 K. The irradiation-induced chemical processing of these ices was monitored online and in situ via Fourier transform infrared spectroscopy to probe the newly formed products quantitatively. The sulfur-bearing molecules produced during the irradiation were sulfur dioxide (SO{sub 2}), sulfur trioxide (SO{sub 3}), and carbonyl sulfide (OCS). Formations of carbon dioxide (CO{sub 2}), carbonmonoxide (CO), and ozone (O{sub 3}) were observed as well. To fit the temporal evolution of the newly formed products and to elucidate the underlying reaction pathways, kinetic reaction schemes were developed and numerical sets of rate constants were derived. Our studies suggest that carbon disulfide (CS{sub 2}) can be easily transformed to carbonyl sulfide (OCS) via reactions with suprathermal atomic oxygen (O), which can be released from oxygen-containing precursors such as water (H{sub 2}O), carbon dioxide (CO{sub 2}), and/or methanol (CH{sub 3}OH) upon interaction with ionizing radiation. This investigation corroborates that carbonyl sulfide (OCS) and sulfur dioxide (SO{sub 2}) are the dominant sulfur-bearing molecules in interstellar ices.

Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150.ANG. are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150A are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

insolubility, some other zinc compounds were studied. A homogeneous catalyst, bis(ethyl fumarato)zinc, showed similar polycarbonate yield to zinc glutarate, and the method of the catalyst preparation affected its catalytic activity. Only a small amount...

(as well as other gases) is very important as SWCNTs are being considered in chemical sensor applications. It is well established that exposure of the materials to UV light can give rise to various photo-induced phe- nomena such as photo-induced polymerization in poly- meric materials (e.g. [4]) and accelerated

to be selective for comonomer-alternating enchainment in the presence of PhCH2C(O)Co(CO)4 to afford poly-??-peptoids. The mechanistic aspects of the reaction of CO and Nbutylaziridine by means of in situ infrared spectroscopy employing CH3C(O)Co(CO)3L (L = PPh3...

, and Pt by electron-beam evaporation or electroless metal deposition.2,5,11 Single amine-functionalized Cd@Rice are used in this work. These SWCNTs are produced by a laser ablation method using nickel as a catalyst

The present invention generally relates to carbon dioxide (CO.sub.2) sensors. In one embodiment, the present invention relates to a carbon dioxide (CO.sub.2) sensor that incorporates lithium phosphate (Li.sub.3PO.sub.4) as an electrolyte and sensing electrode comprising a combination of lithium carbonate (Li.sub.2CO.sub.3) and barium carbonate (BaCO.sub.3). In another embodiment, the present invention relates to a carbon dioxide (CO.sub.2) sensor has a reduced sensitivity to humidity due to a sensing electrode with a layered structure of lithium carbonate and barium carbonate. In still another embodiment, the present invention relates to a method of producing carbon dioxide (CO.sub.2) sensors having lithium phosphate (Li.sub.3PO.sub.4) as an electrolyte and sensing electrode comprising a combination of lithium carbonate (Li.sub.2CO.sub.3) and barium carbonate (BaCO.sub.3).

An efficient way to decorate multiwalled carbon nanotubes with Ru had been developed. In this method, Ru nanoparticles were prepared by water-in-oil reverse microemulsion, and the produced Ru anchored on MWCNTs. Transmission electron microscopy (TEM) result showed that RuO{sub 2} nanoparticles had the uniform size distribution after electrochemical oxidation. Energy dispersive X-rays (EDX) spectra elucidated the presence of ruthenium oxide in the as-prepared composites after electrochemical oxidation. Cyclic voltammetry result demonstrated that a specific capacitance of deposited ruthenium oxide electrode was significantly greater than that of the pristine MWCNTs electrode in the same medium.

Carbon nanotubes (CNTs) have unique chemical and physical properties. Herein, we report an XPS analysis of a forest of multiwalled CNTs using monochromatic Al K? radiation. Survey scans show only one element: carbon. The carbon 1s peak is centered 284.5 eV. The C 1s envelope also shows the expected ? ? ?* shake-up peak at ca. 291 eV. The valence band and carbon KVV Auger signals are presented. When patterned, the CNT forests can be used as a template for subsequent deposition of metal oxides to make thin layer chromatography plates.1-3

The HAN (hydroxylamine nitrate) process for destruction of nitrite in precipitate hydrolysis produces nitrous oxide (N2O) gas as one of the products. N2O can form flammable mixtures with benzene which is also present due to radiolysis and hydrolysis of tetraphenylborate. Extensive flame modeling and explosion testing was undertaken to define the minimum oxidant for combustion of N2O/benzene using both nitrogen and carbon dioxide as diluents. The attached memorandum interprets and documents the results of the studies.